Exterior reflective mirror element for a vehicular rearview mirror assembly

ABSTRACT

An exterior reflective mirror element suitable for a vehicle includes a transparent glass substrate having a reflector and a visual indicator display disposed to the rear of the substrate. The visual indicator display may be part of a blind spot detection and display system of the vehicle wherein the visual indicator display is actuated to emit light responsive to a detection by a blind spot detection detector of the equipped vehicle of an overtaking vehicle in a side lane adjacent the side of the equipped vehicle. The visual indicator display includes at least a first indicator at a first location to the rear of the exterior reflective mirror element. A first portion of the reflector may be at least partially removed at the first location in order to establish an at least partially transmissive first portion of the exterior reflective mirror element at the first location.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.12/061,795, filed Apr. 3, 2008 (Attorney Docket DON01 P-1433), which isa continuation of U.S. application Ser. No. 11/957,755, filed Dec. 17,2007, now U.S. Pat. No. 7,589,883, which is a continuation of U.S.application Ser. No. 11/653,254, filed Jan. 16, 2007, now U.S. Pat. No.7,349,144, which is a continuation application of U.S. application Ser.No. 10/954,233 filed on Oct. 1, 2004, now U.S. Pat. No. 7,202,987, whichis a continuation of U.S. application Ser. No. 10/197,679 filed Jul. 16,2002, now U.S. Pat. No. 6,855,431, which is a continuation of U.S.application Ser. No. 09/381,856, filed Jan. 27, 2000, now U.S. Pat. No.6,420,036, which is a 35 U.S.C. Section 371 of PCT/US98/05570, filedMar. 26, 1998, which is a continuation-in-part of U.S. application Ser.No. 08/824,501, filed Mar. 26, 1997, now U.S. Pat. No. 5,910,854; andapplication Ser. No. 11/653,254 is a continuation-in-part of U.S.application Ser. No. 11/244,182, filed Oct. 6, 2005, now U.S. Pat. No.7,543,947, which is a continuation of U.S. application Ser. No.10/971,456, filed Oct. 22, 2004, now U.S. Pat. No. 7,004,592, which is acontinuation of U.S. application Ser. No. 09/954,285, filed Sep. 18,2001, abandoned, which is a continuation of U.S. application Ser. No.08/957,027, filed Oct. 24, 1997, abandoned, which is a continuation ofU.S. application Ser. No. 08/429,643, filed Apr. 27, 1995, now U.S. Pat.No. 5,724,187, which is a continuation-in-part of U.S. application Ser.No. 08/238,521,filed May 5, 1994, now U.S. Pat. No. 5,668,663.

BACKGROUND OF THE INVENTION

1. Technical Field of the Invention

The present invention relates to reversibly variable electrochromicdevices for varying the transmittance to light, such as electrochromicrearview mirrors, windows and sun roofs for motor vehicles, reversiblyvariable electrochromic elements therefor and processes for making suchdevices and elements.

2. Brief Description of the Related Technology

Reversibly variable electrochromic devices are known in the art. In suchdevices, the intensity of light (e.g., visible, infrared, ultraviolet orother distinct or overlapping electromagnetic radiation) is modulated bypassing the light through an electrochromic medium. The electrochromicmedium is disposed between two conductive electrodes, at least one ofwhich is typically transparent, which causes the medium to undergoreversible electrochemical reactions when potential differences areapplied across the two electrodes. Some examples of these prior artdevices are described in U.S. Pat. No. 3,280,701 (Donnelly); U.S. Pat.No. 3,451,741 (Manos); U.S. Pat. No. 3,806,229 (Schoot); U.S. Pat. No.4,712,879 (Lynam) (“Lynam I”); U.S. Pat. No. 4,902,108 (Byker) (“BykerI”); and I. F. Chang, “Electrochromic and Electrochemichromic Materialsand Phenomena”, in Nonemissive Electrooptic Displays, 155-96, A. R.Kmetz and F. K. von Willisen, eds., Plenum Press, New York (1976).

Reversibly variable electrochromic media include those wherein theelectrochemical reaction takes place in a solid film or occurs entirelyin a liquid solution. See e.g., Chang.

Numerous devices using an electrochromic medium, wherein theelectrochemical reaction takes place entirely in a solution, are knownin the art. Some examples are described in U.S. Pat. No. 3,453,038(Kissa); U.S. Pat. No. 5,128,799 (Byker) (“Byker II”); Donnelly; Manos;Schoot; Byker I; and commonly assigned U.S. Pat. No. 5,073,012 (Lynam)(“Lynam II”); U.S. Pat. No. 5,115,346 (Lynam) (“Lynam III”); U.S. Pat.No. 5,140,455 (Varaprasad) (“Varaprasad I”); U.S. Pat. No. 5,142,407(Varaprasad) (“Varaprasad II”); U.S. Pat. No. 5,151,816 (Varaprasad)(“Varaprasad III”) and U.S. Pat. No. 5,239,405 (Varaprasad) (“VaraprasadIV”); and commonly assigned U.S. patent application Ser. No. 07/935,784(filed Aug. 27, 1992), now U.S. Pat. No. 5,500,760. Typically, theseelectrochromic devices, sometimes referred to as electrochemichromicdevices, are single-compartment, self-erasing, solution-phaseelectrochromic devices. See e.g., Manos, Byker I and Byker II.

In single-compartment, self-erasing, solution-phase electrochromicdevices, the intensity of the electromagnetic radiation is modulated bypassing through a solution held in a compartment. The solution oftenincludes a solvent, at least one anodic compound and at least onecathodic compound. During operation of such devices, the solution isfluid, although it may be gelled or made highly viscous with athickening agent, and the solution components, including the anodiccompounds and cathodic compounds, do not precipitate. See e.g., Byker Iand Byker II.

Certain of these electrochemichromic devices have presented drawbacks.First, a susceptibility exists for distinct bands of color to formadjacent the bus bars after having retained a colored state over aprolonged period of time. This undesirable event is known assegregation. Second, processing and manufacturing limitations arepresented with electrochemichromic devices containingelectrochemichromic solutions. For instance, in the case ofelectrochemichromic devices which contain an electrochemichromicsolution within a compartment or cavity thereof, the size and shape ofthe electrochemichromic device is limited by the bulges andnon-uniformities which often form in such large area electrochemichromicdevices because of the hydrostatic nature of the liquid solution. Third,from a safety standpoint, in the event an electrochemichromic deviceshould break or become damaged through fracture or rupture, it isimportant for the device to maintain its integrity so that, if thesubstrates of the device are shattered, an electrochemichromic solutiondoes not escape therefrom and that shards of glass and the like areretained and do not scatter about. In the known electrochromic devices,measures to reduce breakage or broken glass scattering include the useof tempered glass and/or a laminate assembly comprising at least twopanels affixed to one another by an adhesive. Such measures control thescattering of glass shards in the event of breakage or damage due, forinstance, to the impact caused by an accident.

Numerous devices using an electrochromic medium, wherein theelectrochemical reaction takes place in a solid layer, are known in theart. Typically, these devices employ electrochromic solid-state thinfilm technology [see e.g., N. R. Lynam, “Electrochromic AutomotiveDay/Night Mirrors”, SAE Technical Paper Series, 870636 (1987); N. R.Lynam, “Smart Windows for Automobiles”, SAE Technical Paper Series,900419 (1990); N. R. Lynam and A. Agrawal, “Automotive Applications ofChromogenic Materials”, Large Area Chromogenics: Materials & Devices forTransmittance Control, C. M. Lampert and C. G. Granquist, eds., OpticalEng'g Press, Washington (1990); C. M. Lampert, “Electrochromic Devicesand Devices for Energy Efficient Windows”, Solar Enercry Materials, 11,1-27 (1984); U.S. Pat. No. 3,521,941 (Deb); U.S. Pat. No. 4,174,152(Giglia); Re. 30,835 (Giglia); U.S. Pat. No. 4,338,000 (Kamimori); U.S.Pat. No. 4,652,090 (Uchikawa); U.S. Pat. No. 4,671,619 (Kamimori); LynamI; and commonly assigned U.S. Pat. No. 5,066,112 (Lynam) (“Lynam IV”)and U.S. Pat. No. 5,076,674 (Lynam) (“Lynam V”)].

In solid-state thin film electrochromic devices, an anodicelectrochromic layer and a cathodic electrochromic layer, each layerusually made from inorganic metal oxides, are typically separate anddistinct from one another and assembled in a spaced-apart relationship.The solid-state thin films are often formed using techniques such aschemical vapor deposition or physical vapor deposition. Such techniquesare not attractive economically, however, as they involve cost. Inanother type of solid-state thin film electrochromic device, twosubstrates are coated separately with compositions of photo- orthermo-setting monomers or oligomers to form on one of the substrates anelectrochromic layer, with the electrochromic material present withinthe layer being predominantly an inorganic material, and on the othersubstrate a redox layer. [See Japanese Patent Document JP 63-262,624].

Attempts have been made to prepare electrochromic media from polymers.For example, it has been reported that electrochromic polymer layers maybe prepared by dissolving in a solvent organic polymers, which containno functionality capable of further polymerization, together with anelectrochromic compound, and thereafter casting or coating the resultingsolution onto an electrode. It has been reported further thatelectrochromic polymer layers are created upon evaporation of thesolvent by pressure reduction and/or temperature elevation. [See e.g.,U.S. Pat. No. 3,652,149 (Rogers), U.S. Pat. No. 3,774,988 (Rogers) andU.S. Pat. No. 3,873,185 (Rogers); U.S. Pat. No. 4,550,982 (Hirai);Japanese Patent Document JP 52-10,745; and Y. Hirai and C. Tani,“Electrochromism for Organic Materials in Polymeric All-Solid StateSystems”, Appl. Phys. Lett., 43(7), 704-05 (1983)]. Use of such polymersolution casting systems has disadvantages, however, including the needto evaporate the solvent prior to assembling devices to form polymerelectrochromic layers. This additional processing step adds to the costof manufacture through increased capital expenditures and energyrequirements, involves potential exposure to hazardous chemical vaporsand constrains the type of device to be manufactured.

A thermally cured polymer gel film containing a single organicelectrochromic compound has also been reported for use in displaydevices. [See H. Tsutsumi et al., “Polymer Gel Films with Simple OrganicElectrochromics for Single-Film Electrochromic Devices”, J. Polym. Sci.,30, 1725-29 (1992) and H. Tsutsumi et al., “Single Polymer Gel FilmElectrochromic Device”, Electrochemica Acta, 37, 369-70 (1992)]. The gelfilm reported therein was said to possess a solvent-like environmentaround the electrochromic compounds of that film. This gel film wasreported to turn brown, and ceased to perform color-bleach cycles, afteronly 35,200 color-bleach cycles.

SUMMARY OF THE INVENTION

The present invention also provides novel electrochromic monomercompositions comprising anodic electrochromic compounds, cathodicelectrochromic compounds, a monomer component and a plasticizer that areuseful in the formation of such polychromic solid films. Morespecifically, each of the electrochromic compounds are organic ororganometallic compounds. Electrochromic monomer compositions may alsoinclude, but are not limited to, either individually or in combination,cross-linking agents, photoinitiators, photosensitizers, ultravioletstabilizing agents, electrolytic materials, coloring agents, spacers,anti-oxidizing agents, flame retarding agents., heat stabilizing agents,compatibilizing agents, adhesion promoting agents, coupling agents,humectants and lubricating agents.

The present invention further provides novel processes for makingpolychromic solid films by transforming such novel electrochromicmonomer compositions into polychromic solid films through exposure toelectromagnetic radiation for a time sufficient to effect an in situcure.

The present invention still further provides electrochromic devices,such as those referred to above, particularly rearview mirrors, windowsand sun roofs for automobiles, which devices are stable to outdoorweathering, particularly weathering observed due to prolonged exposureto ultraviolet radiation from the sun, and are safety protected againstimpact from an accident. Such outdoor weathering and safety benefits areachieved by manufacturing these devices using as a medium of varyingtransmittance to light the polychromic solid films prepared by the insitu cure of an electrochromic monomer composition containing a monomercomponent that is capable of further polymerization.

The present invention provides for the first time, among other things(1) polychromic solid films that may be transformed from electrochromicmonomer compositions by an in situ curing process through exposure toelectromagnetic radiation, such as ultraviolet radiation; (2) atransformation during the in situ curing process from the low viscosity,typically liquid, electrochromic monomer compositions to polychromicsolid films that occurs with minimum shrinkage and with good adhesion tothe contacting surfaces; (3) polychromic solid films that (a) may bemanufactured to be self-supporting and subsequently laminated betweenconductive substrates, (b) perform well under prolonged coloration, (c)demonstrate a resistance to degradation caused by environmentalconditions, such as outdoor weathering and all-climate exposure,particularly demonstrating ultraviolet stability when exposed to thesun, and (d) demonstrate a broad spectrum of color under an appliedpotential; (4) polychromic solid films that may be manufacturedeconomically and are amenable to commercial processing; (5) polychromicsolid films that provide inherent safety protection not known toelectrochromic media heretofore; and (6) electrochromic monomercompositions that comprise anodic electrochromic compounds and cathodicelectrochromic compounds, which compounds are organic or organometallic.

The self-supporting nature of polychromic solid films provides manybenefits to the electrochromic devices manufactured therewith, includingthe elimination of a compartmentalization means, such as a sealingmeans, since no such means is required to confine or contain apolychromic solid film within an electrochromic device. That polychromicsolid films may be manufactured to be self-supporting also enhancesprocessability, and vitiates obstacles well-recognized in themanufacturing of electrochromic devices containing known electrochromicmedia, especially those that are to be vertically mounted in theirintended use.

Moreover, since the electrochromic compounds are not free to migratewithin polychromic solid films, in contrast to electrochromic compoundspresent within a liquid solution-phase environment, polychromic solidfilms do not pose the segregation concern as do solution-phaseelectrochemichromic devices; rather, polychromic solid films performwell under prolonged coloration.

Further, from a safety perspective, in the event that electrochromicdevices manufactured with polychromic solid films should break or becomedamaged due to the impact from an accident, no liquid is present to seeptherefrom since the polychromic solid films of the present invention areindeed solid. Also, the need to manufacture electrochromic devices withtempered glass, or with at least one of the substrates being of alaminate assembly, to reduce potential lacerative injuries is obviatedsince polychromic solid films, positioned between, and in abuttingrelationship with, the conductive surface of the two substrates, exhibitgood adhesion to the contacting surfaces. Thus, polychromic solid filmsshould retain any glass shards that may be created and prevent them fromscattering. Therefore, a safety protection feature inherent topolychromic solid films is also provided herein, making polychromicsolid films particularly attractive for use in connection withelectrochromic devices, such as mirrors, windows, sun roofs, shadebands, eye glass and the like.

Polychromic solid films embody a novel and useful technology within theelectrochromic art, whose utility will become more readily apparent andmore greatly appreciated by those of skill in the art through a study ofthe detailed description taken in conjunction with the figures whichfollow hereinafter.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a sectional view of an electrochromic device employing anelectrochromic polymeric solid film according to the present invention.

FIG. 2 depicts a perspective view of an electrochromic glazing assemblyaccording to the present invention.

FIG. 3 is a top plan view of a vehicle having a blind spot detectionsystem.

FIG. 4 is a block diagram and partial schematic diagram of a blind spotdetection display system, as viewed by a vehicle operator.

FIG. 5 is the same view as FIG. 3 of an alternative embodiment of ablind spot detection display system.

FIG. 6 is a perspective view of another alternative embodiment of ablind spot detection display system.

The depictions in these figures are for illustrative purposes and thusare not drawn to scale.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the teaching of the present invention, polychromicsolid films may be prepared by exposing an electrochromic monomercomposition to electromagnetic radiation for a time sufficient totransform the electrochromic monomer composition into a polychromicsolid film. This in situ curing process initiates polymerization of, andtypically completely polymerizes, an electrochromic monomer composition,normally in a liquid state, by exposure to electromagnetic radiation toform a polychromic solid film, whose surface and cross-sections aresubstantially tack-free.

The electrochromic monomer compositions are comprised of anodicelectrochromic compounds, cathodic electrochromic compounds, each ofwhich are organic or organometallic compounds, a monomer component and aplasticizer. In addition, cross-linking agents, photoinitiators,photosensitizers, ultraviolet stabilizing agents, electrolyticmaterials, coloring agents, spacers, anti-oxidizing agents, flameretarding agents, heat stabilizing agents, compatibilizing agents,adhesion promoting agents, coupling agents, humectants and lubricatingagents and combinations thereof may also be added. In the preferredelectrochromic monomer compositions, the chosen monomer component may bea polyfunctional monomer, such as a difunctional monomer, trifunctionalmonomer, or a higher functional monomer, or a combination ofmonofunctional monomer and difunctional monomer or monofunctionalmonomer and cross-linking agent. Those of ordinary skill in the art maychoose a particular monomer component or combination of monomercomponents from those recited in view of the intended application so asto impart the desired beneficial properties and characteristics to thepolychromic solid film.

An anodic electrochromic compound suitable for use in the presentinvention may be selected from the class of chemical compoundsrepresented by the following formulae:

wherein A is O, S or NRR₁;wherein R and R₁ may be the same or different, and each may be selectedfrom the group consisting of H or any straight- or branched-chain alkylconstituent having from about one carbon atom to about eight carbonatoms, such as CH₃, CH₂CH₃, CH₂CH₂CH₃, CH(CH₃)₂, C(CH₃)₃ and the like;provided that when A is NRR₁, Q is H, OH or NRR₁; further provided thatwhen A is NRR₁ a salt may be associated therewith; still furtherprovided that when both A and Q are NRR₁, A and Q need not, but may, bethe same functional group;

D is O, S, NR₁ or Se;

E is R₁, COOH or CONH₂; or, E and T, when taken together, represent anaromatic ring structure having six ring carbon atoms when viewed inconjunction with the ring carbon atoms to which they are attached;

G is H;

J is H, any straight- or branched-chain alkyl constituent having fromabout one carbon atom to about eight carbon atoms, such as CH₃, CH₂CH₃,CH₂CH₂CH₃, CH(CH₃)₂, C(CH₃)₃ and the like, NRR₁,

OR₁, phenyl, 2,4-dihydroxyphenyl or any halogen; or, G and J, when takentogether, represent an aromatic ring structure having six ring carbonatoms when viewed in conjunction with the ring carbon atoms to whichthey are attached;

L is H or OH;

M is H or any halogen;

T is R₁, phenyl or 2,4-dihydroxyphenyl; and

Q is H, OH or NRR₁;

provided that when L and/or Q are OH, L and/or Q may also be saltsthereof; further provided that in order to render it electrochemicallyactive in the present context, anodic electrochromic compound I has beenpreviously contacted with a redox agent;

wherein X and Y may be the same or different, and each may be selectedfrom the group consisting of H, any halogen or NRR₁, wherein R and R₁may be the same or different, and are as defined supra; or, X and Y,when taken together, represent an aromatic ring structure having sixring carbon atoms when viewed in conjunction with the ring carbon atomsto which they are attached; and

Z is OH or NRR¹, or salts thereof; provided that in order to render itelectrochemically active in the present context, anodic electrochromiccompound II has been previously contacted with a redox agent;

wherein R and R₁ may be the same or different, and are defined supra;

wherein R and R₁ may be the same or different, and are defined supra;

wherein R and R₁ may be the same or different, and are defined supra;

Metallocenes suitable for use as a component of the electrochromicmonomer composition include, but are not limited to the following:

wherein R and R₁ may be the same or different, and each may be selectedfrom the group consisting of H; any straight- or branched-chain alkylconstituent having from about 1 carbon atom to about 8 carbon atoms,such as CH₃, CH₂CH₃, CH₂CH₂CH₃, CH(CH₃)₂, C(CH₃)₃ and the like; acetyl;vinyl; allyl; —(CH₂)_(n)—OH, wherein n may be an integer in the range of0 to about 20;

wherein n may be an integer in the range of 0 to about 20; —(CH₂)—COOR₂,wherein n may be an integer in the range of 0 to about 20 and R₂ may beany straight- or branched-chain alkyl constituent having from about 1carbon atom to about 20 carbon atoms, hydrogen, lithium, sodium,

wherein n may be an integer from 0 to about 20, —(CH₂)_(n′)—OR₃, whereinn′ may be an integer in the range of 1 to about 12 and R₃ may be anystraight- or branched-chain alkyl constituent having from about 1 carbonatom to about 8 carbon atoms,

and —(CH₂)—N⁺(CH₃)₃X,

wherein n′ may be an integer in the range of 1 to about 12; X may beCl⁻, Br⁻, I⁻, PF₆ ⁻, ClO₄ ⁻ BF₄ ⁻; and wherein M_(C), is Fe, Ni, Ru, Co,Ti, Cr, W, Mo and the like;

and combinations thereof.

Phenothiazines suitable for use as a component of the electrochromicmonomer composition include, but are not limited to, those representedby the following structures:

where R₉ may be selected from the group consisting of H; any straight-or branched-chain alkyl constituent having from about 1 carbon atom toabout 10 carbon atoms; phenyl; benzyl; —(CH₂)₂—CN; —(CH₂)₂—COOH;

allyl;

wherein m′ may be an integer in the range of 1 to about 8;

wherein R₁₈ may be any straight- or branched-chain alkyl constituenthaving from about 1 carbon atom to about 8 carbon atoms; and

R₁₀, 12₁₁, R₁₂, R₁₃, R₁₄, Ro, R₁₆, and R₁₇ may be selected from H, Cl,Br, CF₃, CH₃, NO₂, COOH, OH, SCH₃, OCH₃, O₂CCH₃ or

R₉ and R₁₇, when taken together, form a ring with six atoms (five ofwhich being carbon) having a carbonyl substituent on one of the carbonatoms. Preferred among phenothiazines 1-A is phenothiazines 2-A to 4-Aas depicted in the following structure:

An example of a desirable quinone for use as component in theelectrochromic monomer composition include, but is not limited to thefollowing structure:

Combinations of components in the electrochromic monomer composition maybe selectively chosen to achieve a desired substantially non-spectralselectivity when the electrochromic element (and the mirror in which theelectrochromic element is to function) is dimmed to a colored state.

To render anodic electrochromic compounds I and II electrochemicallyactive in the context of the present invention, a redox pre-contactingprocedure must be used. Such a redox pre-contacting procedure isdescribed in the context of preparing anodic compounds forelectrochemichromic solutions in Varaprasad IV and commonly assignedU.S. patent application Ser. No. 07/935,784 (filed Aug. 27, 1992), nowU.S. Pat. No. 5,500,760.

Preferably, anodic electrochromic compound I may be selected from thegroup consisting of the class of chemical compounds represented by thefollowing formulae:

and combinations thereof.

Among the especially preferred anodic electrochromic compounds I areMVTB (XV), PT (XVI), MPT (XVII), and POZ (XIX), with MVTB and MPT beingmost preferred. Also preferred is the reduced form of MPT which resultsfrom the redox pre-contacting procedure referred to above, and has beenthereafter isolated. This reduced and isolated form of MPT—RMPT[XVII(a)]—is believed to be 2-methyl-3-hydroxyphenathiazine, which isrepresented by the following chemical formula

and salts thereof.

In addition, a preferred anodic electrochromic compound II is

Likewise, preferred among anodic electrochromic compound III are5,10-dihydro-5,10-dimethylphenazine (“DMPA”) and5,10-dihydro-5,10-diethylphenazine (“DEPA”), with DMPA beingparticularly preferred.

As a preferred anodic electrochromic compound VI, metallocenes, such asferrocene, wherein M_(e) is iron and R and R₁ are each hydrogen, andalkyl derivatives thereof, may also be used advantageously in thecontext of the present invention.

The salts referred to in connection with the anodic electrochromiccompounds include, but are not limited to, alkali metal salts, such aslithium, sodium, potassium and the like. In addition, when A is NRR₁,tetrafluoroborate (“BF₄”), perchlorate (“ClO₄”), trifluoromethanesulfonate (“CF₃S0₃ ⁻”), hexafluorophosphate (“PF₆ ⁻”), acetate (“Ac⁻”)and any halogen may be associated therewith. Moreover, the ring nitrogenatom in anodic electrochromic compound I may also appear as an N-oxide.

Any one or more of anodic electrochromic compounds I, II, III, IV, V, VIor VII may also be advantageously combined, in any proportion, within anelectrochromic monomer composition and thereafter transformed into apolychromic solid film to achieve the results so stated herein. Ofcourse, as regards anodic electrochromic compounds I and II, it isnecessary to contact those compounds with a redox agent prior to use soas to render them electrochemically active in the present invention.Upon the application of a potential thereto, such combinations of anodicelectrochromic compounds within a polychromic solid film may oftengenerate color distinct from the color observed from polychromic solidfilms containing individual anodic electrochromic compounds. A preferredcombination of anodic electrochromic compounds in this invention is thecombination of anodic electrochromic compounds III and VI. Nonetheless,those of ordinary skill in the art may make appropriate choices amongindividual anodic electrochromic compounds and combinations thereof, toprepare a polychromic solid film capable of generating a color suitablefor a particular application.

A choice of a cathodic electrochromic compound for use herein shouldalso be made. The cathodic electrochromic compound may be selected fromthe class of chemical compounds represented by the following formulae:

wherein R₃, R₄, R₂₁, R₂₂, R₂₃ and R₂₄ may be the same or different andeach may be selected from the group consisting of H, any straight- orbranched-chain alkyl constituent having from about one carbon atom toabout eight carbon atoms, or any straight- or branched-chain alkyl- oralkoxy-phenyl, wherein the alkyl or alkoxy constituent contains fromabout one carbon atom to about eight carbon atoms;

wherein n′ may be an integer in the range-of 1 to 12;

wherein R₅ may be H or CH₃, and n′ may be an integer in the range of 1to 12; HO— (CH₂)_(n)—, wherein n′ may be an integer in the range of 1 to12; and HOOC—(CH₂)n′—, wherein n′ may be an integer in the range of 1 to12;

wherein q may be an integer in the range of 0 to 12; wherein each p isindependently an integer from 1 to 12; and wherein X is selected fromthe group consisting of BF₄ ⁻, ClO₄ ⁻, Cf₃SO₃ ⁻, styrylsulfonate(“SS⁻”), 2-acrylamido-2-methylpropane-sulfonate, acrylate, methacrylate,3-sulfopropylacrylate, 3-sulfopropylmethacrylate, PF₆ ⁻, Ac⁻,HO—(R₂₅)—SO₃ ⁻ and HOOC—(R₂₅)—SO₃ ⁻ wherein R₂₅ can be any straight- orbranched-chain alkyl constituent having from about 1 carbon atom toabout 8 carbon atoms, an aryl or a functionalized aryl, an alkyl or arylamide, a branched or linear chain polymer, such as polyvinyls,polyethers and polyesters bearing at least one and preferably multiple,hydroxyl and sulphonate functionalities and any halide; and combinationsthereof.

In one preferred embodiment R₂₅ can be:

or the copolymer derived from acrylamidomethylpropanesulfonic acid(AMPS) and caprolactone acrylate.

Specific cathodic electrochromic compounds useful in the context of thepresent invention include:

Preferably, R₃ and R₄ are ethyl, n-heptyl, hydroxyhexyl orhydroxyundecyl. Thus, when X is PF₆ ⁻, ClO₄ ⁻ or BF₄ ⁻, preferredcathodic electrochromic compounds are ethylviologen perchlorate(“EVClO₄”), heptylviologen tetrafluoroborate (“HVBF₄”), hydroxyundecylviologen hexafluorophosphate (“HUVPF₆”), ethylhydroxyundecyl viologenperclorate (“EHUVClO₄”), hydroxyhexyl viologen hexafluorophosphate(“HHVPF₆”), divalericacid viologen hexafluorophosphate (“DVAVPF₆”),hydroxyundecylphenylpropyl viologen diperchlorate (“HUPPVCL0₄”), anddiphenylpropyl viologen diperchlorate (“PPVCL04”).

The above anodic electrochromic compounds and cathodic electrochromiccompounds may be chosen so as to achieve a desired color, when thepolychromic solid film in which they are present (and the device inwhich the polychromic solid film is contained) is colored to a dimmedstate. For example, electrochromic automotive mirrors manufactured withpolychromic solid films should preferably bear a blue or substantiallyneutral color when colored to a dimmed state. And, electrochromicoptically attenuating contrast filters, such as contrast enhancementfilters, manufactured with polychromic solid films should preferablybear a substantially neutral color when colored to a dimmed state.

The plasticizer chosen for use in the present invention should maintainthe homogeneity of the electrochromic monomer compositions while beingprepared, used and stored, and prior to, during and after exposure toelectromagnetic radiation. As a result of its combination within theelectrochromic monomer composition or its exposure to electromagneticradiation, the plasticizer of choice should not form by-products thatare capable of hindering, or interfering with, the homogeneity and theelectrochemical efficacy of the resulting polychromic solid film. Theoccurrence of any of these undesirable events during the in situ curingprocess, whether at the pre-cure, cure or post-cure phase of the processfor preparing polychromic solid films, may interfere with the processitself, and may affect the appearance and effectiveness of the resultingpolychromic solid films, and the electrochromic devices manufacturedwith the same. The plasticizer also may play a role in defining thephysical properties and characteristics of the polychromic solid filmsof the present invention, such as toughness, flex modulus, coefficientof thermal expansion, elasticity, elongation and the like.

Suitable plasticizers for use in the present invention include, but arenot limited to, triglyme, tetraglyme, acetonitrile, benzylacetone,3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile,butylene carbonate, propylene carbonate, ethylene carbonate, glycerinecarbonate, 2-acetylbutyrolactone, cyanoethyl sucrose, γ-butyrolactone,2-methylglutaronitrile, N,N′-dimethylformamide, 3-methylsulfolane,methylethyl ketone, cyclopentanone, cyclohexanone,4-hydroxy-4-methyl-2-pentanone, acetophenone, glutaronitrile,3,3′-oxydipropionitrile, 2-methoxyethyl ether, triethylene glycol dimethyl ether and combinations thereof. Particularly preferredplasticizers among that group are benzylacetone, 3-hydroxypropionitrile,propylene carbonate, ethylene carbonate, 2-acetylbutyrolactone,cyanoethyl sucrose, triethylene glycol dimethyl ether, 3-methylsulfolaneand combinations thereof.

To prepare a polychromic solid film, a monomer should be chosen as amonomer component that is capable of in situ curing through exposure toelectromagnetic radiation, and that is compatible with the othercomponents of the electrochromic monomer composition at the variousstages of the in situ, curing process. The combination of a plasticizerwith a monomer component (with or without the addition of a difunctionalmonomer or a cross-linking agent) should preferably be in an equivalentratio of between about 75:25 to about 10:90 to prepare polychromic solidfilms with superior properties and characteristics. Of course, theart-skilled should bear in mind that the intended application of apolychromic solid film will often dictate its particular properties andcharacteristics, and that the choice and equivalent ratio of thecomponents within the electrochromic monomer composition may need to bevaried to attain a polychromic solid film with the desired propertiesand characteristics.

Among the monomer components that may be advantageously employed in thepresent invention are monomers having at least one reactivefunctionality rendering the compound capable of polymerization orfurther polymerization by an addition mechanism, such as vinylpolymerization or ring opening polymerization. Included among suchmonomers are oligomers and polymers that are capable of furtherpolymerization. For monomers suitable for use herein, see generallythose commercially available from Monomer-Polymer Labs., Inc.,Philadelphia, Pa.; Sartomer Co., Exton, Pa.; and Polysciences, Inc.,Warrington, Pa.

Monomers capable of vinyl polymerization, suitable for use herein, haveas a commonality the ethylene functionality, as represented below:

wherein R₆, R₇ and R₈ may be the same or different, and are eachselected from a member of the group consisting of hydrogen; halogen;alkyl, cycloalkyl, poly-cycloalkyl, heterocycloalkyl and alkyl andalkenyl derivatives thereof; alkenyl, cycloalkenyl, cycloalkadienyl,poly-cycloalkadienyl and alkyl and alkenyl derivatives thereof;hydroxyalkyl; hydroxyalkenyl; alkoxyalkyl; alkoxyalkenyl; cyano; amido;phenyl; benzyl and carboxylate, and derivatives thereof.

Preferred among these vinyl monomers are the ethylene carboxylatederivatives known as acrylates—i.e., wherein at least one of R₆, R₇ andR₈ are carboxylate groups or derivatives thereof. Suitable carboxylatederivatives include, but are not limited to alkyl, cycloalkyl,poly-cycloalkyl, heterocycloalkyl and alkyl and alkenyl derivativesthereof; alkenyl, cycloalkenyl, poly-cycloalkenyl and alkyl and alkenylderivatives thereof; mono- and poly-hydroxyalkyl; mono- andpolyhydroxyalkenyl; alkoxyalkyl; alkoxyalkenyl and cyano.

Among the acrylates that may be advantageously employed herein are mono-and poly-acrylates (bearing in mind that poly-acrylates function ascross-linking agents as well, see infra), such as 2-hydroxyethylacrylate, 2-hydroxyethyl methacrylate, methylene glycol monoacrylate,diethylene glycol monomethacrylate, 2-hydroxypropyl acrylate,2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropylmethacrylate, dipropylene glycol monomethacrylate, 2,3-dihydroxypropylmethacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate,i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, n-pentylacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethylmethacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butylmethacrylate, s-butyl methacrylate, n-pentyl methacrylate, s-pentylmethacrylate, methoxyethyl acrylate, methoxyethyl methacrylate,triethylene glycol monoacrylate, glycerol monoacrylate, glycerolmonomethacrylate, allyl methacrylate, benzyl acrylate, caprolactoneacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethoxyethylacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy) ethylacrylate,glycidyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, isobornylacrylate, isobornyl methacrylate, i-decyl acrylate, i-decylmethacrylate, i-octyl acrylate, lauryl acrylate, lauryl methacrylate,2-methoxyethyl acrylate, n-octyl acrylate, 2-phenoxyethyl acrylate,2-phenoxyethyl methacrylate, stearyl acrylate, stearyl methacrylate,tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tridecylmethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate,1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate,diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethyleneglycol diacrylate, ethoxylated bisphenol A dimethacrylate, ethyleneglycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, polyethylene glycol diacrylate, polyethylene glycoldimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycoldimethacrylate, triethylene glycol diacrylate, triethylene glycoldimethacrylate, tripropylene glycol diacrylate, dipentaerythritolpentaacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritoltetraacrylate, pentaerythritol triacrylate, trimethylolpropanetriacrylate, trimethyloipropane trimethacrylate,tris(2-hydroxyethyl)-isocyanurate triacrylate,tris(2-hydroxyethyl)-isocyanurate trimethacrylate, polyethylene glycolmonoacrylate, polyethylene glycol monomethacrylate, polypropylene glycolmonoacrylate, polypropylene glycol monomethacrylate, hydroxyethylcellulose acrylate, hydroxyethyl cellulose methacrylate, methoxypoly(ethyleneoxy) ethylacrylate, methoxy poly(ethyleneoxy)ethylmethacrylate and combinations thereof. For a further recitation ofsuitable acrylates for use herein, see those acrylates availablecommercially from Monomer-Polymer Labs, Inc.; Polysciences, Inc. andSartomer Co. Also, those of ordinary skill in the art will appreciatethat derivatized acrylates in general should provide beneficialproperties and characteristics to the resulting polychromic solid film.

Other monomers suitable for use herein include styrenes, unsaturatedpolyesters, vinyl ethers, acrylamides, methyl acrylamides and the like.

Other monomers capable of addition polymerization include isocyanates,polyols, amines, polyamines, amides, polyamides, acids, polyacids,compounds comprising an active methylene group, ureas, thiols, etc,Preferably, such monomers have a functionality of 2 or greater. Forexample, the monomer composition can include isocyanates such ashexamethylene diisocyanate (HDI); toluene diisocyanate (TDI including 2,4 and 2, 6 isomers); diphenylmethane diisocyanate (MDI); isocyanatetipped prepolymers such as those prepared from a diisocyanate and apolyol; condensates produced from hexamethylene diisocyanate includingbiuret type and trimer type (also known as isocyanurate), as is known inthe urethane chemical art. A recitation of various monomers suitable touse in the electrochromic monomer composition is given in the followingTable 1.

TABLE 1 Monomers suitable to use in the electrochromic-monomercomposition Type Tradename Product No: Supplier Location IsocyanateTolonate HDT (Isocyanurate) Rhone-Poulenc Inc. Princeton, NJ IsocyanateTolonate HDB (Biuret) Rhone-Poulene Inc. Princeton, NJ IsocyanateISONATE modified MDI Dow Chemical Midland, MI Isocyanate PAPI polymericMDI Dow Chemical Midland, MI Isocyanate RUBINATE 9043 MDI ICI SterlingHeights, MI Isocyanate DESMODUR N-,100 Miles Pittsburgh, PA IsocyanateTYCEL 7351 Liofol Co. Cary, NC Polyol VORANOL polyether polyols DowChemical Midland, MI Polyol VORANOL copolymer polyols Dow ChemicalMidland, MI Polyol ARCOL E-786 Arco Chemical Hinsdale, IL Polyol ARCOLLHT-112 Arco Chemical Hinsdale, IL Polyol ARCOL E-351 Arco ChemicalHinsdale, IL Polyol LEXOREZ 1931-50 Inolex Chemical Co. Philadelphia, PAPolyol LEXOREZ 1842-90 Inolex Chemical Co. Philadelphia, PA PolyolLEXOREZ 1405-65 Inolex Chemical Co. Philadelphia, PA Polyol LEXOREZ1150-110 Inolex Chemical Co. Philadelphia, PA, Polyol DESMOPHEN 1700Miles Pittsburgh, PA Tin Catalyst DABCO T-9 Air Products and ChemicalInc. Allentown, PA Tin Catalyst DABCO T-1 Air Products and Chemical Inc.Allentown, PA Tin Catalyst DABCO T-120 Air Products and Chemical Inc.Allentown, PA

In situ cure can be facilitated by inclusion of organometallic catalystsin the electrochromic monomer composition. Examples of such catalystsinclude dibutyl tin dilaurate, dibutyl tin, diacetate, and dibutyl tindioctoate. Other catalysts can include organometallic compounds ofbismuth, iron, tin, titanium, cobalt, nickel, antimony, vanadium,cadmium, mercury, aluminum, lead, zinc, barium, and thorium. Also,amines such as tertiary amines can be used.

Monomers capable of ring opening polymerization suitable for use hereininclude epoxides, lactones, lactams, dioxepanes, spiro orthocarbonates,unsaturated spiro orthoesters and the like.

Preferred among these ring opening polymerizable monomers are epoxidesand lactones. Of the epoxides suitable for use herein, preferred arecyclohexene oxide, cyclopentene oxide, glycidyl i-propyl ether, glycidylacrylate, furfuryl glycidyl ether, styrene oxide, ethyl-3-phenylglycidate, 1,4-butanediol glycidyl ether,2,3-epoxypropyl-4-(2,3-epoxypropoxy)benzoate,4,4′-bis-(2,3-epoxypropoxy)biphenyl and the like.

Also, particularly preferred are the cycloalkyl epoxides sold under the“CYRACURE” tradename by Union Carbide Chemicals and Plastics Co., Inc.,Danbury, Conn., such as the “CYRACURE” resins UVR-6100 (mixed cycloalkylepoxides), UVR-6105 (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), UVR-6110 (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate) and UVR-6128 [ bis-(3,4-epoxycyclohexyl)adipate], and the“CYRACURE” diluents UVR-6200 (mixed cycloalkyl epoxides) and UVR-6216(1,2-epoxyhexadecane); those epoxides commercially available from DowChemical Co., Midland, Mich., such as D.E.R. 736 epoxy resin(epichlorohydrin-polyglycol reaction product), D.E.R. 755 epoxy resin(diglycidyl ether of bisphenol A-diglycidyl ether of polyglycol) andD.E.R. 732 epoxy resin (epichlorohydrin-polyglycol reaction product),and the NOVOLAC epoxy resins such as D.E.N. 431, D.E.N. 438 and D.E.N.439 (phenolic epoxides), and those epoxides commercially available fromShell Chemical Co., Oak Brook, Ill., like the “EPON” resins 825 and 100°F. (epichlorohydrin-bisphenol A type epoxy resins).

Other commercially available epoxide monomers that are particularlywell-suited for use herein include those commercially available underthe “ENVIBAR” tradename from Union Carbide Chemicals and Plastics Co.,Inc., Danbury, Conn., such as “ENVIBAR” UV 1244 (cycloalkyl epoxides).

In addition, derivatized urethanes, such as acrylated (e.g., mono- orpoly-acrylated) urethanes; derivatized heterocycles, such as acrylated(e.g., mono- or poly-acrylated) heterocycles, like acrylated epoxides,acrylated lactones, acrylated lactams; and combinations thereof, capableof undergoing addition polymerizations, such as vinyl polymerizationsand ring opening polymerizations, are also well-suited for use herein.

Many commercially available ultraviolet curable formulations arewell-suited for use herein as a monomer component in the electrochromicmonomer composition. Among those commercially available ultravioletcurable formulations are acrylated urethanes, such as the acrylatedalkyl urethane formulations commercially available from Sartomer Co.,including Low Viscosity Urethane Acrylate (Flexible) (CN 965), LowViscosity Urethane Acrylate (Resilient) (CN 964), Urethane Acrylate (CN980), Urethane Acrylate/TPGDA (CN 966 A80), Urethane Acrylate/IBOA (CN966 J75), Urethane Acrylate/EOEOEA (CN 966H90), Urethane Acrylate/TPGDA(CN 965 A80), Urethane Acrylate/EOTMPTA (CN 964 E75), UrethaneAcrylate/EOEOEA (CN 966H90), Urethane Acrylate/TPGDA (CN 963 A80),Urethane Acrylate/EOTMPTA (CN 963 E75), Urethane Acrylate (Flexible) (CN962), Urethane Acrylate/EOTMPTA (CN 961 E75), Urethane Acrylate/EOEOEA(CN 961 H90), Urethane Acrylate (Hard) (CN 955), Urethane Acrylate(Hard) (CN 960) and Urethane Acrylate (Soft) (CN 953), and acrylatedaromatic urethane formulations, such as those sold by Sartomer Co., mayalso be used herein, including Hydrophobic Urethane Methacrylate (CN974), Urethane Acrylate/TPGDA (CN 973 A80), Urethane Acrylate/IBOA (CN973 J75), Urethane Acrylate/EOEOEA (CN 973H90), Urethane Acrylate(Flexible) (CN 972), Urethrane Acrylate (Resilient) (CN 971), UrethaneAcrylate/TPGDA (CN 971 A80), Urethane Acrylate/TPGDA (CN 970 A60),Urethane Acrylate/EOTMPTA (CN 970 E60) and Urethane Acrylate/EOEOEA (CN974H75). Other acrylated urethane formulations suitable for use hereinmay be obtained commercially from Monomer-Polymer Labs, Inc. andPolysciences, Inc.

Other ultraviolet curable formulations that may be used herein are theultraviolet curable acrylated epoxide formulations commerciallyavailable from Sartomer Co., such as Epoxidized Soy Bean, Oil Acrylate(CN 111), Epoxy Acrylate (CN 120), Epoxy Acrylate/TPGDA (CN 120 A75),Epoxy Acrylate/HDDA (CN 120 B80), Epoxy Acrylate/TMPTA (CN 120 C80),Epoxy Acrylate/GPTA (CN 120 D80), Epoxy Acrylate/Styrene (CN 120 S85),Epoxy Acrylate (CN 104), Epoxy Acrylate/GPTA (CN 104 D80), EpoxyAcrylate/HDDA (CN 104 B80), Epoxy Acrylate/TPGDA (CN 104 A80), EpoxyAcrylate/TMPTA (CN 104 C75), Epoxy Novolac Acrylate/TMPTA (CN 112 C60),Low Viscosity Epoxy Acrylate (CN 114), Low Viscosity EpoxyAcrylate/EOTMPTA (CN 114 E80), Low Viscosity Epoxy Acrylate/GPTA (CN 114D75) and Low Viscosity EpoxyAcrylate/TPGDA CN 114 A80).

In addition, “SARBOX” acrylate resins, commercially available fromSartomer Co., like Carboxylated Acid Terminated (SB 400), CarboxylatedAcid Terminated (SB 401), Carboxylated Acid Terminated (SB 500),Carboxylated Acid Terminated (SB 500E50), Carboxylated Acid Terminated(SB 500K60), Carboxylated Acid Terminated (SB 501), Carboxylated AcidTerminated (SB 510E35), Carboxylated Acid Terminated (SB 520E35) andCarboxylated Acid Terminated (SB 600) may also be advantageouslyemployed herein.

Also well-suited for use herein are ultraviolet curable formulationslike the ultraviolet curable conformational coating formulationscommercially available under the “QUICK CURE” trademark from theSpecialty Coating Systems subsidiary of Union Carbide Chemicals &Plastics Technology Corp., Indianapolis, Ind., and sold under theproduct designations B-565, B-566, B-576 and BT-5376; ultraviolet curingadhesive formulations commercially available from Loctite Corp.,Newington, Conn. under the product names UV OPTICALLY CLEAR ADH, MULTIPURPOSE UV ADHESIVE, “IMPRUV” LV POTTING COMPOUND and “LOCQUIC”ACTIVATOR 707; ultraviolet curable urethane formulations commerciallyavailable from Norland Products, Inc., New Brunswick, N.J., and soldunder the product designations “NORLAND NOA 61”, “NORLAND NOA 65” and“NORLAND NOA 68”; and ultraviolet curable acrylic formulationscommercially available from Dymax Corp., Torrington, Conn., including“DYMAX LIGHT-WELD 478”.

By employing polyfunctional monomers, like difunctional monomers, orcross-linking agents, cross-linked polychromic solid films may beadvantageously prepared.

Such cross-linking tends to improve the physical properties andcharacteristics (e.g., mechanical strength) of the resulting polychromicsolid films. Cross-linking during cure to transform the electrochromicmonomer composition into a polychromic solid film may be achieved bymeans of free radical ionic initiation by the exposure toelectromagnetic radiation. This may be accomplished by combiningtogether all the components of the particular electrochromic monomercomposition and thereafter effecting cure. Alternatively, cross-linksmay be achieved by exposing to electromagnetic radiation theelectrochromic monomer composition for a time sufficient to effect apartial cure, whereupon further electromagnetic radiation and/or athermal influence may be employed to effect a more complete in situ cureand transformation into the polychromic solid film.

Suitable polyfunctional monomers for use in preparing polychromic filmsshould have at least two reactive functionalities, and may be selectedfrom, among others, ethylene glycol diacrylate, ethylene glycoldimethacrylate, 1,2-butylene dimethacrylate, 1,3-butylenedimethacrylate, 1,4-butylene dimethacrylate, propylene glycoldiacrylate, propylene glycol dimethacrylate, diethylene glycoldiacrylate, dipropylene glycol diacrylate, divinyl benzene, divinyltoluene, diallyl tartrate, allyl maleate, divinyl tartrate, triallylmelamine, glycerine trimethacrylate, diallyl maleate, divinyl ether,diallyl monomethylene glycol citrate, ethylene glycol vinyl allylcitrate, allyl vinyl maleate, diallyl itaconate, ethylene glycol diesterof itaconic acid, polyester of maleic anhydride with triethylene glycol,polyallyl glucoses (e.g., triallyl glucose), polyallyl sucroses (e.g.,pentaallyl sucrose diacrylate), glucose dimethacrylate, pentaerythritoltetraacrylate, sorbitol dimethacrylate, diallyl aconitate, divinylcitrasonate, diallyl fumarate, allyl methacrylate and polyethyleneglycol diacrylate.

Ultraviolet radiation absorbing monomers may also be advantageouslyemployed herein. Preferred among such monomers are1,3-bis-(4-benzoyl-3-hydroxyphenoxy)-2-propylacrylate,2-hydroxy-4-acryloxyethoxybenzophenone, 2-hydroxy-4-octoxybenzophenoneand 4-methacryloxy-2-hydroxybenzophenone, as they perform the dualfunction of acting as a monomer component, or a portion thereof, and asan ultraviolet stabilizing agent.

Further, ultraviolet absorbing layers may be coated onto, or adhered to,the first substrate and/or second substrate, and preferably thesubstrate closest to the source of UV radiation, to assist in shieldingthe electrochromic device from the degradative effect of ultravioletradiation. Suitable ultraviolet absorbing layers include those recitedin U.S. Pat. No. 5,073,012 entitled “Anti-scatter, UltravioletProtected, Anti-misting Electro-optical Assemblies”, filed Mar. 20,1990, or as disclosed in U.S. patent application Ser. No. 08/547,578filed Oct. 24, 1995, now U.S. Pat. No. 5,729,379, the disclosures ofwhich are hereby incorporated by reference herein.

Examples of such layers include a layer of DuPont BE1028D which is apolyvinylbutyral/polyester composite available from E.I. DuPont deNemours and Company, Wilmington, Del., and SORBALITE™ polymeric UVblockers (available from Monsanto Company, St. Louis, Mo.) whichcomprise a clear thin polymer film, with UV absorbingchromophores-incorporated, such as by covalent bonding, in a polymerbackbone. The SORBALITE™ clear thin polymer film when placed on asurface of the substrate closest to the source of UV radiation (such asthe sun), efficiently absorbs UV light below about 370 nm with minimaleffect on the visible region. Thickness of the SORBALITE™ film isdesirably in the range of about 0.1 microns to 1000 microns (orthicker); preferably less than 100 microns; more preferably less thanabout 25 microns, and most preferably less than about 10 microns. Also,UV absorbing thin films or additives such as cerium oxide, iron oxide,nickel oxide and titanium oxide or such oxides with dopants can be usedto protect the electrochromic device from UV degradation. Further asdescribed above, UV absorbing chromophores can be incorporated, such asby covalent bonding, into the solid polymer matrix to impart enhancedresilience to UV radiation. Also near-infrared radiation absorbingspecies may be incorporated into the solid polymer matrix.

The density of the cross-link within the resulting polychromic solidfilm tends to increase with the amount and/or the degree offunctionality of polyfunctional monomer present in the electrochromicmonomer composition. Cross-linking density within a polychromic solidfilm may be achieved or further increased by adding to theelectrochromic monomer composition cross-linking agents, whichthemselves are incapable of undergoing further polymerization. Inaddition to increasing the degree of cross-linking within the resultingpolychromic solid film, the use of such cross-linking agents in theelectrochromic monomer composition may enhance the prolonged colorationperformance of the resulting polychromic solid film. Included among suchcross-linking agents are polyfunctional hydroxy compounds, such asglycols and glycerol, polyfunctional primary or secondary aminocompounds and polyfunctional mercapto compounds. Among the preferredcross-linking agents are pentaerythritol,2-ethyl-2-(hydroxymethyl)-1,3-propanediol, the poly (caprolactone) diolshaving molecular weights of 1,250, 2,000 and 3,000, and polycarbonatediol available from Polysciences, Inc. and the polyfunctional hydroxycompounds commercially available under the “TONE” tradename from UnionCarbide Chemicals and Plastics Co. Inc., Danbury, Conn., such ass-caprolactone triols (known as “TONE” 0301, “TONE” 0305 and “TONE”0310). Among the preferred glycols are the poly(ethylene glycols), likethose sold under the “CARBOWAX” tradename by the Industrial Chemicaldivision of Union Carbide Corp., Danbury, Conn. such as “CARBOWAX” PEG200, PEG 300, PEG 400, PEG 540 Blend, PEG 600, PEG 900, PEG 1000, PEG1450, PEG 3350, PEG 4600, and PEG 8000, with “CARBOWAX” PEG 1450 beingthe most preferred among this group, and those available fromPolysciences, Inc.

Polychromic solid films that perform well under prolonged coloration maybe prepared from electrochromic monomer compositions that contain as amonomer component at least some portion of a polyfunctionalmonomer—e.g., a difunctional monomer. By preferably using polyfunctionalmonomers having their functional groups spaced apart to such an extentso as to enhance the flexibility of the resulting polychromic solidfilm, polychromic films may be prepared with a minimum of shrinkageduring the transformation process and that also perform well underprolonged coloration.

While it is preferable to have electrochromic monomer compositions whichcontain a monomer component having polyfunctionality in preparingpolychromic solid films that perform well under prolonged coloration,electrochromic monomer compositions that exhibit enhanced resistance toshrinkage when transformed into polychromic solid films preferablycontain certain monofunctional monomers. In this regard, depending onthe specific application, some physical properties and characteristicsof polychromic solid films may be deemed of greater import than others.Thus, superior performance in terms of resistance to shrinkage during insitu, curing of the electrochromic monomer composition to thepolychromic solid film may be balanced with the prolonged colorationperformance of the resulting polychromic solid film to achieve theproperties and characteristics desirable of that polychromic solid film.

Those of ordinary skill in the art may make appropriate choices amongthe herein described monomers—monofunctional and polyfunctional, such asdifunctional—and cross-linking agents to prepare a polychromic solidfilm having beneficial properties and characteristics for the specificapplication by choosing such combinations of a monofunctional monomer toa polyfunctional monomer or a monofunctional monomer to a cross-linkingagent in an equivalent ratio of about 1:1 or greater.

In the preferred electrochromic monomer compositions, photoinitiators orphotosensitizers may also be added to assist the initiation of the insitu curing process. Such photoinitiators or photsensitizers enhance therapidity of the curing process when the electrochromic monomercompositions are exposed to electromagnetic radiation. These materialsinclude, but are not limited to, radical initiation type and cationicinitiation type polymerization initiators such as benzoin derivatives,like the n-butyl, i-butyl and ethyl benzoin alkyl ethers, and thosecommercially available products sold under the “ESACURE” tradename bySartomer Co., such as “ESACURE” TZT (trimethyl benzophenone blend), KB1(benzildimethyl ketal), KB60 (60′^(%) solution of benzildimethyl ketal),EB3 (mixture of benzoin n-butyl ethers), KIP 100F (α-hydroxy ketone),KT37 (TZT and α-hydroxy ketone blend), ITX (i-propylthioxanthone), X15(ITX and TZT blend), and EDB [ethyl-4-(dimethylamino)-benzoate]; thosecommercially available products sold under the “IRGACURE” and “DAROCURE”tradenames by Ciba Geigy Corp., Hawthorne, N.Y., specifically “IRGACURE”184, 907, 369, 500, 651, 261, 784 and “DAROCURE” 1173 and 4265,respectively; the photoinitiators commercially available from UnionCarbide Chemicals and Plastics Co. Inc., Danbury, Conn., under the“CYRACURE” tradename, such as “CYRACURE” UVI-6974 (mixed triarylsulfonium hexafluoroantimonate salts) and UVI-6990 (mixed triarylsulfonium hexafluorophosphate salts); and the visible light [blue]photoinitiator, dl-camphorquinone.

Of course, when those of ordinary skill in the art choose a commerciallyavailable ultraviolet curable formulation, it may no longer be desirableto include as a component within the electrochromic monomer compositionan additional monomer to that monomer component already present in thecommercial formulation. And, as many of such commercially availableultraviolet curable formulations contain a photoinitiator orphotosensitizer, it may no longer be desirable to include this optionalcomponent in the electrochromic monomer composition. Nevertheless, amonomer, or a photoinitiator or a photosensitizer, may still be added tothe electrochromic monomer composition to achieve beneficial results,and particularly when specific properties and characteristics aredesired of the resulting polychromic solid film.

With an eye toward maintaining the homogeneity of the electrochromicmonomer composition and the polychromic solid film which results afterin situ cure, those of ordinary skill in the art should choose theparticular components dispersed throughout, and their relativequantities, appropriately. One or more compatibilizing agents may beoptionally added to the electrochromic monomer composition so as toaccomplish this goal. Such compatibilizing agents include, among others,combinations of plasticizers recited herein, a monomer component havingpolyfunctionality and cross-linking agents that provide flexiblecross-links. See supra.

Further, monomer compositions can be formed comprising both organic andinorganic monomers. For example, inorganic monomers such astetraethylorthosilicate, titanium isopropoxide, metal alkoxides, and thelike may be included in the monomer composition, and formation of thesolid matrix (be it an organic polymer matrix, an inorganic polymermatrix or an organic/inorganic polymer matrix) can proceed via a varietyof reaction mechanisms, including hydrolysis/condensation reactions.Also, transition metal-peroxy acid products (such as tungsten peroxyacid product) can be reacted with alcohol to form a peroxy-transitionmetal derivative (such as peroxytungstic ester derivative), with arecitation of such species being found in U.S. Pat. No. 5,457,218entitled “Precursor and Related Method of Forming ElectrochromicCoatings”, invented by J. Cronin et al and issued Oct. 10, 1995, thedisclosure of which is hereby incorporated by reference herein, and canbe used as a component of the electrochromic monomer composition. Also,the polychromic solid films may optionally be combined with inorganicand organic films such as those of metal oxides (e.g., WO₃, NiO, IrO₂,etc.) and organic films such a polyaniline. Examples of such films arefound in U.S. patent application Ser. No. 08/429,643 filed Apr. 27,1995, now U.S. Pat. No. 5,724,187, U.S. patent application Ser. No.08/547,578 filed Oct. 24, 1995, now U.S. Pat. No. 5,729,379, and U.S.patent application Ser. No. 08/330,090 filed Oct. 26, 1994, now U.S.Pat. No. 5,780,160, the disclosures of which are hereby incorporated byreference herein. Also, the devices of this present invention canbenefit from the use of elemental semiconductors layers or stacks, PRM,anti-wetting adaption, synchronous manufacturing, multi-layertransparent conducting stacks incorporating a thin metal layerovercoated with a conducting metal oxide (such as a high reflectivityreflector comprising around 1000 Å of silver metal or aluminum metal,overcoated with about 1500 Å of ITO and with a reflectivity greater than70% R and a sheet resistance below 5 ohms/square), conducting seals,variable intensity band pass filters, isolation valve vacuumbackfilling, cover sheets and on demand displays such as are disclosedin U.S. patent application Ser. No. 08/429,643 filed Apr. 27, 1995, nowU.S. Pat. No. 5,724,187, the disclosure of which is hereby incorporatedby referenc herein. Also, as further disclosed in U.S. patentapplication Ser. No. 08/429,643, now U.S. Pat. No. 5,724,187, the solidpolymer films of this present invention may comprise within theirstructure electrochromatically active phthalocyanine-based and/orphthalocyanine-derived moieties including transition metalphthalocyanines such as zirconium phthalocyanine and molybdenumphthalocyanine. Also, the solid polymer films of this invention can becombined with an electron donor (e.g., TiO₂)— spacer (salicylic acid orphosphoric acid bound to the TiO₂)— electron acceptor (a viologen boundto the salicylic acid or to the phosphoric acid) heterodyad such asdescribed also in U.S. patent application Ser. No. 08/429,643, now U.S.Pat. No. 5,724,187. Such donor-spacer-acceptor solid films can functionas an electrochromic solid film in combination with the polychromicsolid films of the present invention. Further, such as described in U.S.patent application Ser. No. 08/429,643, now U.S. Pat. No. 5,724,187,such chemically modified nanoporous-nanocrystalline films, such as ofTiO₂ with absorbed redox chromophores, can be used in a variety ofelectrochromic devices and device constructions, including rearviewmirrors, glazings, architectural and vehicular glazings, displays,filters, contrast enhancement filters and the like.

Many electrochromic compounds absorb electromagnetic radiation in theabout 290 nm to about 400 nm ultraviolet region. Because solar radiationincludes an ultraviolet region between about 290 mm to about 400 nm, itis often desirable to shield such electrochromic compounds fromultraviolet radiation in that region. By so doing, the longevity andstability of the electrochromic compounds may be improved. Also, it isdesirable that the polychromic solid film itself be stable toelectromagnetic radiation, particularly in that region. This may beaccomplished by adding to the electrochromic monomer composition anultraviolet stabilizing agent (and/or a self-screening plasticizer whichmay act to block or screen such ultraviolet radiation) so as to extendthe functional lifetime of the resulting polychromic solid film. Suchultraviolet stabilizing agents (and/or self-screening plasticizers)should be substantially transparent in the visible region and functionto absorb ultraviolet radiation, quench degradative free radicalreaction formation and prevent degradative oxidative reactions.

As those of ordinary skill in the art will readily appreciate, thepreferred ultraviolet stabilizing agents, which are usually employed ona by-weight basis, should be selected so as to be compatible with theother components of the electrochromic monomer composition, and so thatthe physical, chemical or electrochemical performance of, as well as thetransformation into, the resulting polychromic solid film is notadversely affected.

Although many materials known to absorb ultraviolet radiation may beemployed herein, preferred ultraviolet stabilizing agents include“UVINUL” 400 [2,4-dihydroxybenzophenone (manufactured by BASF Corp.,Wyandotte, Mich.)], “UVINUL” D 49[2,2′-dihydroxy-4,4′-dimethoxybenzophenone (BASF Corp.)], “UVINUL” N 35[ethyl-2-cyano-3,3-diphenylacrylate (BASF Corp.)], “UVINUL” N 539[2-ethylhexyl-2-cyano-3,3′diphenylacrylate (BASF Corp.)], “UVINUL” M 40[2-hydroxy-4-methoxybenzophenone (BASF Corp.)], “UVINUL” M 408[2-hydroxy-4-octoxybenzophenone (BASF Corp.)], “TINUVIN” P[2-(2′-hydroxy-5′-methylphenyl)-triazole (Ciba Geigy Corp.)], “TINUVIN”327 [2-(3′,5′-di-t-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole (CibaGeigy Corp.)], “TINUVIN” 328[2-(3′,5′-di-n-pentyl-2′-hydroxyphenyl)-benzotriazole (Ciba GeigyCorp.)] and “CYASORB UV” 24 [2,2′-dihydroxy-4-methoxy-benzophenone(manufactured by American Cyanamid Co., Wayne, N.J.)], with “UVINUL” M40, “UVINUL” M 408, “UVINUL” N 35 and “UVINUL” N 539 being the mostpreferred ultraviolet stabilizing agents when used in a by-weight rangeof about 0.1%, to about 15%, with about 4% to about 10% being preferred.

Since solar radiation includes an ultraviolet region only between about290 nm and 400 μm, the cure wave length of the electrochromic monomercomposition, the peak intensity of the source of electromagneticradiation, and the principle absorbance maxima of the ultravioletstability agents should be selected to provide a rapid and efficienttransformation of the electrochromic monomer compositions into thepolychromic solid films, while optimizing the continued long-termpost-cure stability to outdoor weathering and all-climate exposure ofpolychromic solid films.

An electrolytic material may also be employed in the electrochromicmonomer composition to assist or enhance the conductivity of theelectrical current passing through the resulting polychromic solid film.The electrolytic material may be selected from a host of knownmaterials, preferred of which are tetraethylammonium perchlorate,tetrabutylammonium tetrafluoroborate, tetrabutylammoniumhexafluorophosphate, tetrabutylammonium trifluoromethane sulfonate,lithium salts and combinations thereof, with tetrabutylammoniumhexafluorophosphate and tetraethylammonium perchlorate being the mostpreferred.

In addition, adhesion promoting agents or coupling agents may be used inthe preferred electrochromic monomer compositions to further enhance thedegree to which the resulting polychromic solid films adhere to thecontacting surfaces. Adhesion promoting or coupling agents, whichpromote such enhanced adhesion, include silane coupling agents, andcommercially available adhesion promoting agents like those sold bySartomer Co., such as Alkoxylated Trifunctional Acrylate (9008),Trifunctional Methacrylate Ester (9010 and 9011), Trifunctional AcrylateEster (9012), Aliphatic Monofunctional Ester (9013 and 9015) andAliphatic Difunctional Ester (9014). Moreover, carboxylated vinylmonomers, such as methacrylic acid, vinyl carboxylic acid and the likemay be used to further assist the development of good adhesion to thecontacting surfaces.

And, coloring agents, spacers, anti-oxidizing agents, flame retardingagents, heat stabilizing agents and combinations thereof may be added tothe electrochromic monomer compositions, choosing of course thosematerials in appropriate quantities depending upon the specificapplication of the resulting polychromic solid film. For instance, ablue-tinted electrochromic automotive mirror, such as described herein,may be prepared by dispersing within the electrochromic monomercomposition a suitable ultraviolet stable coloring agent, such as“NEOZAPON” BLUE™ 807 (a phthalocyanine blue dye, available commerciallyfrom BASF Corp., Parsippany, N.J.) and “NEOPEN” 808 (a phthalocyanineblue dye, available commercially from BASF Corp.).

Polychromic solid films may be prepared within an electrochromic deviceby introducing an electrochromic monomer composition to a film formingmeans, such as the vacuum backfilling technique, which fills a cavity ofan assembly by withdrawing into the cavity the electrochromic monomercomposition while the assembly is in an environment of reducedatmospheric pressure [see e.g., Varaprasad II], the two hole fillingtechnique, where the electrochromic monomer composition is dispensedunder pressure into the assembly through one hole while a gentle vacuumis applied at the other hole [see e.g., Varaprasad III], or with thesandwich lamination technique, which contemporaneously creates and fillsa cavity of an assembly by placing on one or both substrates either athermoplastic sealing means to act as a spacing means [see commonlyassigned U.S. Pat. No. 5,233,461 (Dornan)] or glass beads of nominaldiameter, and then exposing to electromagnetic radiation at least oneclear substrate of the assembly constructed by any of the abovemanufacturing techniques (containing the low viscosity electrochromicmonomer composition) for a time sufficient to transform theelectrochromic monomer composition into a polychromic solid film.

In connection with such film forming means, spacers, such as glassbeads, may be dispensed across the conductive surface of one or bothsubstrates, or dispersed throughout the electrochromic monomercomposition which may then be dispensed onto the conductive surface ofone or both substrates, to assist in preparing a polychromic solid filmwhich contacts, in abutting relationship, the conductive surface of thetwo substrates. Similarly, a pre-established spacing means of solidmaterial, such as tape, pillars, walls, ridges and the like, may also beemployed to assist in determining the interpane distance between thesubstrates in which a polychromic solid film may be prepared to contact,in abutting relationship with, the conductive surface of the twosubstrates.

Polychromic solid films may also be prepared separately from theelectrochromic device, and thereafter placed between, and in abuttingrelationship with, the conductive surface of the two substrates used inconstructing the device. Many known film manufacturing processes may beemployed as a film forming means to manufacture polychromic solid films.Included among these processes are calendering, casting, rolling,dispensing, coating, extrusion and thermoforming. For a non-exhaustivedescription of such processes see Modern Plastics Encyclopedia 1988,203-300, McGraw-Hill Inc., New York (1988). For instance, theelectrochromic monomer composition may be dispensed or coated onto theconductive surface of a substrate, using conventional techniques, suchas curtain coating, spray coating, dip coating, spin coating, rollercoating, brush coating or transfer coating.

As described above, polychromic solid films may be prepared as aself-supporting solid film which may thereafter be contacted withconductive substrates.

For instance, an electrochromic monomer composition may be continuouslycast or dispensed onto a surface, such as a fluorocarbon surface and thelike, to which the polychromic solid film, transformed therefrom byexposure to electromagnetic radiation, does not adhere. In this way,polychromic solid films may be continuously prepared, and, for example,reeled onto a take-up roller and stored for future use. Thus, when aparticular electrochromic device is desired, an appropriately shapedportion of the stored polychromic solid film may be cut from the rollusing a die, laser, hot wire, blade or other cutting means. This nowcustom-cut portion of polychromic solid film may be contacted with theconductive substrates to form an electrochromic device.

For example, the custom-cut portion of the polychromic solid film may belaminated between the conductive surface of two transparent conductivecoated substrates, such as ITO or tin oxide coated glass substrates, twoITO or tin oxide coated “MYLAR” [polyethylene terephthalate film(commercially available from E.I. du Pont de Nemours and Co.,Wilmington, Del.)] substrates or one ITO or tin oxide coated glasssubstrate and one ITO or tin oxide coated “MYLAR” substrate. To thisend, it may be desirable to allow for residual cure in the storedpolychromic solid film so that adhesion to the conductive substrates inthe laminate to be formed is facilitated and optimized.

In this regard, a polychromic solid film may be prepared by the filmforming means of extrusion or calendaring wherein the electrochromicmonomer composition is transformed into the polychromic solid film byexposure to electromagnetic radiation prior to, contemporaneously with,or, if the electrochromic monomer composition is sufficiently viscous,after passing through the extruder or calendar. Thereafter, thepolychromic solid film may be placed between, and in abuttingrelationship with, the conductive surface of the substrates, and thenconstruction of the electrochromic device may be completed.

While preparing polychromic solid films, the viscosity of theelectrochromic monomer composition may be controlled to optimize itsdispensibility by adjusting the temperature of (1) the electrochromicmonomer composition itself, (2) the substrates on which theelectrochromic monomer composition may be placed to assemble theelectrochromic device or (3) the processing equipment used to preparepolychromic solid films (if the polychromic film is to be preparedindependently from the substrates of the electrochromic devices). Forexample, the temperature of the electrochromic monomer composition, thesubstrates or the equipment or combinations thereof may be elevated todecrease the viscosity of the electrochromic monomer composition.Similarly, the uniformity on the substrate of the dispensedelectrochromic monomer composition may be enhanced using laminationtechniques, centrifuge techniques, pressure applied from the atmosphere(such as with vacuum bagging), pressure applied from a weighted object,rollers and the like.

The substrates employed in the electrochromic devices of the presentinvention may be constructed from materials that are substantiallyinflexible as well as flexible depending on the application to whichthey are to be used. In this regard, the substrates may be constructedfrom substantially inflexible substrates, such as glass, laminatedglass, tempered glass, optical plastics, such as polycarbonate, acrylicand polystyrene, and flexible substrates, such as “MYLAR” film. Also,the glass substrates suitable for use herein may be tinted specializedglass which is known to significantly reduce ultraviolet radiationtransmission while maintaining high visible light transmission. Suchglass, often bearing a blue colored tint provides a commerciallyacceptable silvery reflection to electrochromic automotive mirrors evenwhen the polychromic solid film is prepared containing an ultravioletstabilizing agent or other component which may have a tendency to imbuea yellowish appearance to the polychromic solid film. Preferably, bluetinted specialized glass may be obtained commercially from PittsburghPlate Glass Industries, Pittsburgh, Pa. as “SOLEXTRA” 7010; Ford GlassCo., Detroit, Mich. as “SUNGLAS” Blue; or Asahi Glass Co., Tokyo, Japanunder the “SUNBLUE” tradename.

Whether the chosen substrate is substantially inflexible or flexible, atransparent conductive coating, such as indium tin oxide (“ITO”) ordoped-tin oxide, is coated on a surface of the substrate making thatsurface suitable for placement in abutting relationship with apolychromic solid film.

The choice of substrate may influence the choice of processingtechniques used to prepare the polychromic solid film or the type ofelectrochromic device assembled. For example, when assembling anelectrochromic device from flexible substrates, an electrochromicmonomer composition may be advantageously applied to such flexiblesubstrates using a roll-to-roll system where the flexible substrates arereleased from rolls (that are aligned and rotate in directions oppositeto one another), and brought toward one another in a spaced-apartrelationship. In this way, the electrochromic monomer composition may bedispensed or injected onto one of the flexible substrates at the pointwhere the two flexible substrates are released from their respectiverolls and brought toward one another, while being contemporaneouslyexposed to electromagnetic radiation for a time sufficient to transformthe electrochromic monomer composition into a polychromic solid film.

The dispensing of the electrochromic monomer composition may be effectedthrough a first injection nozzle positioned over one of the rolls offlexible substrate. A weathering barrier forming material, such as acuring epoxide like an ultraviolet curing epoxide, may be dispensed inan alternating and synchronized manner onto that flexible substratethrough a second injection nozzle positioned adjacent to the firstinjection nozzle. By passing in the path of these nozzles as acontinuously moving ribbon, a flexible substrate may be contacted withthe separate polymerizable compositions in appropriate amounts andpositions on the flexible substrate.

In manufacturing flexible electrochromic assemblies having a dimensionthe full width of the roll of flexible substrate, a weathering barrierforming material may be dispensed from the second injection nozzle whichmay be positioned inboard (typically about 2 mm to about 25 mm) from theleftmost edge of the roll of flexible substrate. The first injectionnozzle, positioned adjacent to the second injection nozzle, may dispensethe electrochromic monomer composition onto most of the full width ofthe roll of flexible substrate. A third injection nozzle, alsodispensing weathering barrier forming material, may be positionedadjacent to, but inboard from, the rightmost edge of that roll offlexible substrate (typically about 2 mm to about 25 mm). In thismanner, and as described above, a continuous ribbon of a flexibleelectrochromic assembly may be formed (upon exposure to electromagneticradiation) which, in turn, may be taken up onto a take-up roller. By sodoing, a flexible electrochromic assembly having the width of the rollof flexible substrate, but of a particular length, may be obtained byunrolling and cutting to length an electrochromic assembly of aparticular size.

Should it be desirable to have multiple flexible electrochromicassemblies positioned in the same take-up roll, multiple nozzles may beplaced appropriately at positions throughout the width of one of therolls of flexible substrate, and the dispensing process carried outaccordingly.

In that regard, a small gap (e.g., about 5 mm to about 50 mm) should bemaintained where no dispensing occurs during the introduction of theelectrochromic monomer composition and the weathering barrier formingmaterial onto the substrate so that a dead zone is created where neitherthe electrochromic monomer composition nor the weathering barrierforming material is present. Once the weathering barrier and polychromicsolid film have formed (see infra), the electrochromic assembly may beisolated by cutting along the newly created dead zones of the flexibleassemblies. This zone serves conveniently as a cutting area to formelectrochromic assemblies of desired sizes.

And, the zones outboard of the respective weathering barriers serve asconvenient edges for attachment of a means for introducing an appliedpotential to the flexible electrochromic assemblies, such as bus bars.Similarly, the bisection of the dead zones establishes a convenientposition onto which the bus bars may be Affixed.

While each of the weathering barrier forming material and theelectrochromic monomer composition may be transformed into a weatheringbarrier and a polychromic solid film, respectively, by exposure toelectromagnetic radiation, the required exposures to complete therespective transformations may be independent from one another. Theweathering barrier forming material may also be thermally cured to formthe weathering barrier.

The choice of a particular electromagnetic radiation region to effect insitu cure may depend on the particular electrochromic monomercomposition to be cured. In this regard, typical sources ofelectromagnetic radiation, such as ultraviolet radiation, include:mercury vapor lamps; xenon arc lamps; “H”, “D”, “X”, “M”, “V” and “A”fusion lamps (such as those commercially available from Fusion UV CuringSystems, Buffalo Grove, Ill.); microwave generated ultravioletradiation; solar power and fluorescent light sources. Any of theseelectromagnetic radiation sources may use in conjunction therewithreflectors and filters, so as to focus the emitted radiation within aparticular electromagnetic region. Similarly, the electromagneticradiation may be generated directly in a steady fashion or in anintermittent fashion so as to minimize the degree of heat build-up.Although the region of electromagnetic radiation employed to in situcure the electrochromic monomer compositions into polychromic solidfilms is often referred to herein as being in the ultraviolet region,that is not to say that other regions of radiation within theelectromagnetic spectrum may not also be suitable. For instance, incertain situations, visible radiation may also be advantageouslyemployed.

Bearing in mind that some or all of the components of the electrochromicmonomer composition may inhibit, retard or suppress the in situ curingprocess, a given source of electromagnetic radiation should have asufficient intensity to overcome the inhibitive effects of thosecomponents so as to enable to proceed successfully the transformation ofthe electrochromic monomer composition into the polychromic solid film.By choosing a lamp with a reflector and, optionally, a filter, a sourcewhich itself produces a less advantageous intensity of electromagneticradiation may suffice. In any event, the chosen lamp preferably has apower rating of at least about 100 watts per inch (about 40 watts percm), with a power rating of at least about 300 watts per inch (about 120watts per cm) being particularly preferred. Most preferably, thewavelength of the lamp and its output intensity should be chosen toaccommodate the presence of ultraviolet stabilizing agents incorporatedinto electrochromic monomer compositions. Also, a photoinitiator orphotosensitizer, if used, may increase the rate of in situ, curing orshift the wavelength within the electromagnetic radiation spectrum atwhich in situ curing will occur in the transformation process.

During the in situ curing process, the electrochromic monomercomposition will be exposed to a source of electromagnetic radiationthat emits an amount of energy, measured in K(J/m², determined byparameters including: the size, type and geometry of the source; theduration of the exposure to electromagnetic radiation; the intensity ofthe radiation (and that portion of radiation emitted within the regionappropriate to effect curing); the absorbance of electromagneticradiation by any intervening materials, such as substrates, conductivecoatings and the like; and the distance the electrochromic monomercomposition lies from the source of radiation. Those of ordinary skillin the art will readily appreciate that the polychromic solid filmtransformation may be optimized by choosing appropriate values for theseparameters in view of the particular electrochromic monomer composition.

The source of electromagnetic radiation may remain stationary while theelectrochromic monomer composition passes through its path.Alternatively, the electrochromic monomer composition may remainstationary while the source of electromagnetic radiation passesthereover or therearound to complete the transformation into apolychromic solid film. Still alternatively, both may traverse oneanother, or for that matter remain stationary, provided that theelectrochromic monomer composition is exposed to the electrochromicradiation for a time sufficient to effect such in situ curing.

Commercially available curing systems, such as the Fusion UV CuringSystems F-300 B [Fusion UV Curing Systems, Buffalo Grove, Ill.], HanoviaUV Curing System [Hanovia Corp., Newark, N.J.] and RC-500 A Pulsed UVCuring System [Xenon Corp., Woburn, Mass.], are well-suited toaccomplish the transformation. Also, a Sunlighter UV chamber fitted withlow intensity mercury vapor lamps and a turntable may accomplish thetransformation.

Electromagnetic radiation in the near-infrared and far-infrared(including short and long wavelengths from 3 microns to 30 microns andbeyond) regions of the electromagnetic spectrum can be used, as canradiation in other regions such as microwave radiation. Thus, forelectrochromic monomer compositions responsive to energy input thatincludes thermal energy, radiant heaters that emit in the infraredregion and couple energy into the monomer composition can be used. Forcompositions responsive to microwave energy, a microwave generator canbe used. Also, for systems that respond, for example, to a combinationof energy inputs from different regions of the electromagnetic spectrum,a combined energy radiator can be used. For example, the Fusion UVCuring System, Sunlight UV Chamber, Hanovia UV Curing System, andRC-500A Pulsed UV Curing System described above emit energy efficientlyin both the ultraviolet region and the infrared region, and thus effecta cure both by photoinitiation and thermally. For systems responsive tothermal influences, ovens, lehrs, converyorized ovens, induction ovens,heater banks and the like can be used to couple energy into theelectrochromic monomer composition by convection, conduction and/orradiation. Also, chemical initiators and catalysts, photo initiators,latent curing agents (such as are described in U.S. patent applicationSer. No. 08/429,643, now U.S. Pat. No. 5,724,187, the disclosure ofwhich is hereby incorporated by reference herein) and similar chemicalaccelerants can be used to assist conversion of the electrochromicmonomer composition into a cross-linked solid polymer matrix. Bycustomizing and selecting the components of the electrochromic monomercomposition, cure can be retarded/suppressed until after the compositionis applied within the cavity of the electrochromic cell. Thereafter, byexposure to electromagnetic radiation or thermal influence, cure to thesolid polymer matrix polychromic film can be accelerated. Since deviceswill not typically be consumer used until at least days (often weeks ormonths) after initial application of the monomer composition within theinterpane cell cavity, electrochromic monomer compositions can becomposed that in situ cure at room temperature (typically 15° to 30° C.)over time once established within the interpane cavity (for example,within 24 hours). Alternately, electrochromic devices can be thermallyin situ cured in an oven at a temperature, for example, of 60° C. orhigher for a time period of, for example, five minutes or longer withthe particular oven temperature and oven dwell time being readilyestablished by experimentation for any given electrochromic monomercomposition. For example, we find good results by exposure of the tincatalyzed compositions of the Examples to about 80° C. in an oven forabout two hours. If faster curing systems are desired, then the monomercomposition can be appropriately adjusted, particularly by appropriateselection of the type and concentration of initiators, curing agents,catalysts, cross-linking agents, accelerants, etc.

The required amount of energy may be delivered by exposing theelectrochromic monomer composition to a less powerful source ofelectromagnetic radiation for a longer period of time, through forexample multiple passes, or conversely, by exposing it to a morepowerful source of electromagnetic radiation for a shorter period oftime. In addition, each of those multiple passes may occur with a sourceat different energy intensities. In any event, those of ordinary skillin the art should choose an appropriate source of electromagneticradiation depending on the particular electrochromic monomercomposition, and place that source at a suitable distance therefromwhich, together with the length of exposure, optimizes thetransformation process. Generally, a slower controlled cure, such asthat achieved by multiple passes using a less intense energy source, maybe preferable over a rapid cure using a more intense energy source, forexample, to minimize shrinkage during the transformation process. Also,it is desirable to use a source of electromagnetic radiation that isdelivered in an intermittent fashion, such as by pulsing or strobing, soas to ensure a thorough and complete cure without causing excessive heatbuild-up.

In transforming electrochromic monomer compositions into polychromicsolid films, shrinkage may be observed during and after thetransformation process of the electrochromic monomer composition into apolychromic solid film. This undesirable event may be controlled orlessened to a large extent by making appropriate choices among thecomponents of the electrochromic monomer composition. For instance,appropriately chosen polyfunctional monomers or cross-linking agents mayenhance resistance to shrinkage during the transformation process. Inaddition, a conscious control of the type and amount of plasticizer usedin the electrochromic monomer composition may also tend to enhanceresistance to shrinkage. While shrinkage may also be observed withpolychromic solid films that have been subjected to environmentalconditions, especially conditions of environmental accelerated aging,such as thermal cycling and low temperature soak, a conscious choice ofcomponents used in the electrochromic monomer composition may tend tominimize this event as well. In general, shrinkage may be decreased asthe molecular weight of the monomer employed is increased, and by usingindex matched inert fillers, such as glass beads or fibres.

Electrochromic devices may be manufactured with polychromic solid filmsof a particular thickness by preparing partially-cured polychromic solidfilms between the glass substrates of electrochromic assemblies withspacers or a thermoplastic spacing means having been placed on one orboth of the substrates. This partially-cured polychromic solid filmshould have a thickness slightly greater than that which the resultingpolychromic solid film will desirably assume in the completed device.The electrochromic assemblies should then be subjected to compression,such as that provided by an autoclave/vacuum bagging process, andthereafter be exposed to electromagnetic radiation to complete thetransformation into a polychromic solid film with the desired filmthickness.

FIGS. 1 and 2 show an electrochromic device assembled from thepolychromic solid films of the present invention. The electrochromicassembly 1 includes two substantially planar substrates 2, 3 positionedsubstantially parallel to one another. It is preferable that thesesubstrates 2, 3 be positioned as close to parallel to one another aspossible so as to avoid double imaging, which is particularly noticeablein mirrors, especially when the electrochromic media—i.e., thepolychromic solid film—is colored to a dimmed state.

A source of an applied potential need be introduced to theelectrochromic assembly 1 so that polychromic solid film 6 may color ina rapid, intense and uniform manner. That source may be connected byelectrical leads 8 to conducting strips, such as bus bars 7. The busbars 7 may be constructed of a metal, such as copper, stainless steel,aluminum or solder, or of conductive frits and epoxides, and should beaffixed to a conductive coating 4, coated on a surface of each of thesubstrates 2, 3. An exposed portion of the conductive coating 4 shouldbe provided for the bus bars 7 to adhere by the displacement of thecoated substrates 2, 3 in opposite directions relative to eachother—lateral from, but parallel to—, with polychromic solid film 6positioned between, and in abutting relationship with, the conductivesurface of the two substrates.

As noted above, coated on a surface of each of these substrates 2, 3 isa substantially transparent conductive coating 4. The conductive coating4 is generally from about 300 Å to about 10,000 Å in thickness, having arefractive index in the range of about 1.6 to about 2.2. Preferably, aconductive coating 4 with a thickness of about 1,200 Å to about 2,300 Å,having a refractive index of about 1.7 to about 1.9, is chosen dependingon the desired appearance of the substrate when the polychromic solidfilm situated therebetween is colored.

The conductive coating 4 should also be highly and uniformly conductivein each direction to provide a substantially uniform response as to filmcoloring once a potential is applied. The sheet resistance of thesetransparent conductive substrates 2, 3 may be below about 100 ohms persquare, with about 6 ohms per square to about 20 ohms per square beingpreferred. Such substrates 2, 3 may be selected from among thosecommercially available as glass substrates, coated with indium tin oxide(“ITO”) from Donnelly Corporation, Holland, Mich., or tin oxide-coatedglass substrates sold by the LOF Glass division of Libbey-Owens-FordCo., Toledo, Ohio under the tradename of “TEC-Glass” products, such as“TEC 10” (10 ohms per square sheet resistance), “TEC 12” (12 ohms persquare sheet resistance), “TEC 15” (15 ohms per square sheet resistance)and “TEC 20” (20 ohms per square sheet resistance) tin oxide-coatedglass. Moreover, tin oxide coated glass substrates, commerciallyavailable from Pittsburgh Plate Glass Industries, Pittsburgh, Pa. underthe “SUNGATE” tradename, may be advantageously employed herein.

Also, substantially transparent conductive coated flexible substrates,such as ITO deposited onto substantially clear or tinted “MYLAR”, may beused. Such flexible substrates are commercially available from SouthwallCorp., Palo Alto, Calif.

The conductive coating 4 coated on each of substrates 2, 3 may beconstructed from the same material or different materials, including tinoxide, ITO, ITO-FW, ITO-HW, ITO-HWG, doped tin oxide, such asantimony-doped tin oxide and fluorine-doped tin oxide, doped zinc oxide,such as antimony-doped zinc oxide and aluminum-doped zinc oxide, withITO being preferred.

The substantially transparent conductive coated substrates 2, 3 may beof the full-wave length-type (“FW”) (about 6 ohms per square to about 8ohms per square sheet resistance), the half-wave length-type (“HW”)(about 12 ohms per square to about 15 ohms per square sheet resistance)or the half-wave length green-type (“HWG”) (about 12 ohms per square toabout 15 ohms per square sheet resistance). The thickness of FW is about3,000 Å in thickness, HW is about 1,500 Å in thickness and HWG is about1,960 Å in thickness, bearing in mind that these substantiallytransparent conductive coated substrates 2, 3 may vary as much as about100 to about 200 Å. HWG has a refractive index of about 1.7 to about1.8, and has an optical thickness of about five-eighths wave to abouttwo-thirds wave. HWG is generally chosen for electrochromic devices,especially reflective devices, such as mirrors, whose desired appearancehas a greenish hue in color when a potential is applied.

Optionally, and for some applications desirably, the spaced-apartsubstantially transparent conductive coated substrates 2, 3 may have aweather barrier 5 placed therebetween or therearound. The use of aweather barrier 5 in the electrochromic devices of the present inventionis for the purpose of preventing environmental contaminants fromentering the device during long-term use under harsh environmentalconditions rather than to prevent escape of electrochromic media, suchas with an electrochromic device. Weather barrier “5 may be made frommany known materials, with epoxy resins coupled with spacers,plasticized polyvinyl butyral (available commercially under the “SAFLEX”tradename from Monsanto Co., St. Louis, Mo.), ionomer resins (availablecommercially under the “SURLYN” tradename from E.I. du Pont de Nemoursand Co., Wilmington, Del.) and “KAPTON” high temperature polyamide tape(available commercially from E.I. du Pont de Nemours and Co.,Wilmington, Del.) being preferred. In general, it may be desirable touse within the electrochromic device, and particularly for weatherbarrier 5, materials such as nitrile containing polymers and butylrubbers that form a good barrier against oxygen permeation fromenvironmental exposure.

A further recitation of weather barrier materials and types (includingsingle and double weather barrier constructions) is found in U.S. patentapplication Ser. No. 08/429,643 filed Apr. 27, 1995, now U.S. Pat. No.5,724,187, the disclosure of which is hereby incorporated by referenceherein, including flexible weather barrier materials that are beneficialwhen the polychromic solid film devices of this invention are exposed towide and rapid oscillation between temperature extremes, such as thethermal shocks experienced during normal use in or on a vehicle inregions of climate extremes. Also, devices, such as electrochromicrearview mirrors utilizing a polychromic solid film, can be constructedsuitable for use on automobiles, and suitable to withstand acceleratedaging testing such as boiling in water for an extended period (such as96 hours or longer); exposure to high temperature/high humidity for anextended period (for example, 85° C./85^(%) relative humidity for 720hours or longer); exposure within a steam autoclave for extended periods(for example, 121° C.; 15-18 psi steam for 144 hours or longer).

In the sandwich lamination technique, see supra, it is the thickness ofthe polychromic solid film itself, especially when a highly viscouselectrochromic monomer composition is used, optionally coupled witheither spacers or a thermoplastic spacing means, assembled within theelectrochromic devices of the present invention that determines theinterpane distance of the spaced-apart relationship at which thesubstrates are positioned. This interpane distance may be influenced bythe addition of spacers to the electrochromic monomer composition, whichspacers, when added to an electrochromic monomer composition, assist indefining the film thickness of the resulting polychromic solid film.And, the thickness of the polychromic solid film may be about 10 μm toabout 1000 μm, with about 20 μm to about 200 μm being preferred, a filmthickness of about 37 μm to about 74 μm being particularly preferred,and a film thickness of about 53 μm being most preferred depending ofcourse on the chosen electrochromic monomer composition and the intendedapplication.

By taking appropriate measures, electrochromic devices manufactured withpolychromic solid films may operate so that, upon application of apotential thereto, only selected portions of the device—i.e., throughthe polychromic solid film—will color in preference to the remainingportions of the device. In such segmented electrochromic devices, linesmay be scored or etched onto the conductive surface of either one orboth of substrates 2, 3, in linear alignment so as to cause a break inelectrical continuity between regions immediately adjacent to the break,by means such as chemical etching, mechanical scribing, laser etching,sand blasting and other equivalent means. By so doing, an addressablepixel may be created by the break of electrical continuity when apotential is applied to a predetermined portion of the electrochromicdevice. The electrochromic device colors in only that pre-determinedportion demonstrating utility, for example, as an electrochromic mirror,where only a selected portion of the mirror advantageously colors toassist in reducing locally reflected glare or as an electrochromicinformation display device.

To prepare an electrochromic device containing a polychromic solid film,the electrochromic monomer composition may be dispensed onto theconductive surface of one of the substrates 2 or 3. The conductivesurface of the other substrate may then be placed thereover so that theelectrochromic monomer composition is dispersed uniformly onto andbetween the conductive surface of substrates 2, 3.

This assembly may then be exposed, either in a continuous orintermittent manner, to electromagnetic radiation, such as ultravioletradiation in the region between about 200 nm to about 400 nm for aperiod of about 2 seconds to about 10 seconds, so that theelectrochromic monomer composition is transformed by in situ curing intopolychromic solid film 6. The intermittent manner may include multipleexposures to such energy.

Once the electrochromic device is assembled with polychromic solid film6, a potential may be applied to the bus bars 7 in order to induce filmcoloring. The applied potential may be supplied from a variety ofsources including, but not limited to, any source of alternating current(“AC”) or direct current (“DC”) known in the art, provided that, if allAC source is chosen, control elements, such as diodes, should be placedbetween the source and each of the conductive coatings 4 to ensure thatthe potential difference between the conductive coatings 4 does notchange polarity with variations in polarity of the applied potentialfrom the source. Suitable DC sources are storage batteries, solarthermal cells, photovoltaic cells or photoelectrochemical cells.

An electrochromic device, such as an electrochromic shade band where agradient opacity panel may be constructed by positioning the bus bars 7along the edges of the substrates in such a way so that only aportion—e.g., the same portion—of each of the substrates 2, 3 have thebus bars 7 affixed thereto. Thus, where the bus bars 7 are aligned withone another on opposite substrates 2, 3, the introduction of an appliedpotential to the electrochromic device will cause intense color to beobserved in only that region of the device onto which an electric fieldhas been created—i.e., only that region of the device having the busbars 7 so aligned. A portion of the remaining bleached region will alsoexhibit color extending from the intensely colored region at the busbar/non-bus bar transition gradually dissipating into the remainingbleached region of the device.

The applied potential generated from any of these sources may beintroduced to the polychromic solid film of the electrochromic device inthe range of about 0.001 volts to about 5.0 volts. Typically, however, apotential of about 0.2 volts to about 2.0 volts is preferred, with about1 volt to about 1.5 volts particularly preferred, to permit the currentto flow across and color the polychromic solid film 6 so as to lessenthe amount of light transmitted therethrough. The extent ofcoloring—i.e., high transmittance, low transmittance and intermediatetransmittance levels—at steady state in a particular device will oftendepend on the potential difference between the conductive surface of thesubstrates 2, 3, which relationship permits the electrochromic devicesof the present invention to be used as “gray-scale” devices, as thatterm is used by those of ordinary skill in the art.

A zero potential or a potential of negative polarity (i.e., a bleachingpotential) may be applied to the bus bars 7 in order to induce highlight transmittance through polychromic solid film 6. A zero potentialto about −0.2 volts will typically provide an acceptable response timefor bleaching; nevertheless, increasing the magnitude of the negativepotential to about −0.7 volts will often enhance response times. And, afurther increase in the magnitude of that potential to about −0.8 voltsto about −0.9 volts, or a magnitude of even more negative polarity asthe art-skilled should readily appreciate, may permit polychromic solidfilm 6 to form a light-colored tint while colored to a partial- orfully-dimmed state.

In electrochromic devices where the polychromic solid film is formedwithin the assembly by exposure to electromagnetic radiation, theperformance of the device may be enhanced by applying the positivepolarity of the potential to the substrate that faced theelectromagnetic radiation during the transformation process. Thus, inthe case of electrochromic mirrors manufactured in such a manner, thepositive polarity of the potential should be applied to the conductivesurface of the clear, front glass substrate, and the negative polarityof the potential applied to the conductive surface of the silvered, rearglass substrate, to observe such a beneficial effect.

In the context of an electrochromic mirror assembly, a reflectivecoating, having a thickness in the range of 250 Å to about 2,000 Å,preferably about 1,000 Å, should thereafter be applied to one of thetransparent conductive coated glass substrates 2 or 3 in order to form amirror. Suitable materials for this layer are aluminum, pladium,platinum, titanium, gold, chromium, silver and stainless steel, withsilver being preferred. As an alternative to such metal reflectors,multi-coated thin film stacks of dielectric materials or a high indexsingle dielectric thin film coating may be used as a reflector.Alternatively, one of the conductive coatings 4 may be a metallicreflective layer which serves not only as an electrode, but also as amirror.

It is clear from the teaching herein that should a window, sun roof orthe like be desirably constructed, the reflective coating need only beomitted from the assembly so that the light which is transmitted throughthe transparent panel is not further assisted in reflecting backtherethrough.

Similarly, an electrochromic optically attenuating contrast filter maybe manufactured in the manner described above, optionally incorporatinginto the electrochromic assembly an anti-reflective means, such as acoating, on the front surface of the outermost substrate as viewed by anobserver (see e.g., Lynam V); an anti-static means, such as a conductivecoating, particularly a transparent conductive coating of ITO, tin oxideand the like; index matching means to reduce internal and interfacialreflections, such as thin films of an appropriately selected opticalpath length; and/or light absorbing glass, such as glass tinted to aneutral density, such as “GRAYLITE” gray tinted glass (commerciallyavailable from Pittsburgh Plate Glass Industries, Pittsburgh, Pa.) and“SUNGLAS” Gray gray tinted glass (commercially available from Ford GlassCo., Detroit, Mich.), to augment contrast enhancement. Moreover, polymerinterlayers, which may be tinted gray, such as those used inelectrochromic constructions as described in Lynam III, may beincorporated into such electrochromic optically attenuating contrastfilters.

Electrochromic optical attenuating contrast filters may be an integralpart of a device or may be affixed to an already constructed device,such as cathode ray tube monitors. For instance, an optical attenuatingcontrast filter may be manufactured from a polychromic solid film andthen affixed, using a suitable optical adhesive, to a device that shouldbenefit from the properties and characteristics exhibited by thepolychromic solid film. Such optical adhesives maximize optical qualityand optical matching, and minimize interfacial reflection, and includeplasticized polyvinyl butyral, various silicones, polyurethanes such as“NORLAND NOA 65” and “NORLAND NOA 68”, and acrylics such as “DYMAXLIGHT-WELD 478”. In such contrast filters, the electrochromic compoundsare chosen for use in the polychromic solid film so that theelectrochromic assembly may color to a suitable level upon theintroduction of an applied potential thereto, and no undesirablespectral bias is exhibited. Preferably, the polychromic solid filmshould dim through a substantially neutral colored partial transmissionstate, to a substantially neutral colored full transmission state.

Polychromic solid films may be used in electrochromic devices,particularly glazings and mirrors, whose functional surface issubstantially planar or flat, or that are curved with a convexcurvature, a compound curvature, a multi-radius curvature, a sphericalcurvature, an aspheric curvature, or combinations of such curvature. Forexample, flat electrochromic automotive mirrors may be manufacturedusing the polychromic solid films of the present invention. Also, convexelectrochromic automotive mirrors may be manufactured, with radii ofcurvature typically in the range of about 25″ to about 250″; preferablyin the range of about 35″ to about 100″, as are conventionally known. Inaddition, multi-radius automotive mirrors, such as those described inU.S. Pat. No. 4,449,786 (McCord), may be manufactured using thepolychromic solid films of the present invention. Multi-radiusautomotive mirrors may be used typically on the driver-side exterior ofan automobile to extend the driver's field of view and to enable thedriver to safely see rearward and to avoid blind-spots in the rearwardfield of view. Generally, such mirrors comprise a higher radius (evenflat) region closer to the driver and a lower radius (i.e., more curved)region outboard from the driver that serves principally as theblind-spot detection zone in the mirror.

Indeed, such polychromic solid film-containing electrochromicmulti-radius automotive mirrors may benefit from the prolongedcoloration performance of polychromic solid films and/or from theability to address individual segments in such mirrors.

Often, a demarcation means, such as a silk-screened or otherwise appliedline of black epoxy, may be used to separate the more curved, outboardblind-spot region from the less curved, inboard region of such mirrors.The demarcation means may also include an etching of a deletion line oran otherwise established break in the electrical continuity of thetransparent conductors used in such mirrors so that either one or bothregions may be individually or mutually addressed. Optionally, thisdeletion line may itself be colored black. Thus, the outboard, morecurved region may operate independently from the inboard, less curvedregion to provide an electrochromic mirror that operates in a segmentedarrangement. Upon the introduction of an applied potential, either ofsuch regions may color to a dimmed intermediate reflectance level,independent of the other region, or, if desired, both regions mayoperate together in tandem.

An insulating demarcation means, such as demarcation lines, dots and/orspots, may be placed within electrochromic devices, such as mirrors,glazings, optically attenuating contrast filters and the like, to assistin creating the interpane distance of the device and to enhance overallperformance, in particular the uniformity of coloration across largearea devices. Such insulating demarcation means, constructed from, forexample, epoxy coupled with glass spacer beads, plastic tape or die cutfrom plastic tape, may be placed onto the conductive surface of one ormore substrates by silk-screening or other suitable technique prior toassembling the device. The insulating demarcation means may begeometrically positioned across the panel, such as in a series ofparallel, uniformly spaced-apart lines, and may be clear, opaque, tintedor colorless and appropriate combinations thereof, so as to appeal tothe automotive stylist.

If the interpane distance between the substrates is to be, for example,about 250 μm then the insulating demarcation means (being substantiallynon-deformable) may be screened, acted or adhered to the conductivesurface of a substrate at a lesser thickness, for example, about 150 μmto about 225 μm. Of course, if substantially deformable materials areused as such demarcation means, a greater thickness, for example, about275 μm to about 325 μm may be appropriate as well. Alternatively, theinsulating demarcation means may have a thickness about equal to that ofthe interpane distance of the device, and actually assist in bondingtogether the two substrates of the device.

In any event, the insulating demarcation means should prevent theconductive surfaces of the two substrates (facing one another in theassembled device) from contacting locally one another to avoidshort-circuiting the electrochromic system. Similarly, should theelectrochromic device be touched, pushed, impacted and the like at someposition, the insulating demarcation means, present within the interpanedistance between the substrates, should prevent one of the conductivesurfaces from touching, and thereby short-circuiting, the otherconductive surface. This may be particularly advantageous when flexiblesubstrates, such as ITO-coated “MYLAR”, are used in the electrochromicdevice.

Although spacers may be added to the electrochromic monomer compositionand/or distributed across the conductive surface of one of thesubstrates prior to assembling the device, such random distributionprovides a degree of uncertainty as to their ultimate location withinthe electrochromic device. By using such a screen-on technique asdescribed above, a more defined and predictable layout of the insulatingdemarcation means may be achieved. Further, such spacers may be a rigidinsoluble spacer material such as glass or be rigid soluble spacermaterial (such as a polymer such as polycarbonate,polymethylmethacrylate, polystyrene and the like) capable of dissolvingin the plasticizer of the monomer composition. For example, rigid,soluble polymer spacer beads can be sprinkled across the conductivesurface of a substrate and so help define an interpane spacing when thedevice is first assembled. Then, when the monomer composition isdispensed into the interpane spacing (after the establishment of theinterpane spacing with the assistance of soluble polymer spacers), thenover time the soluble spacer beads dissolve in the plasticizer,preferably prior to in situ conversion to the solid polychromic film.

Using such insulating demarcation means, one or both of the substrates,either prior to or after assembly in the device, may be divided intoseparate regions with openings or voids within the insulatingdemarcation means interconnecting adjacent regions so as to permit aready introduction of the electrochromic monomer composition into theassembly.

A demarcation means may be used that is conductive as well, providedthat it is of a smaller thickness than the interpane distance and/or alayer of an insulating material, such as a non-conductive epoxy,urethane or acrylic, is applied thereover so as to prevent conductivesurfaces from contacting one another and thus short-circuiting theelectrochromic assembly.

Such conductive demarcation means include conductive frits, such assilver frits like the # 7713 silver conductive frit availablecommercially from E.I. de Pont de Nemours and Co., Wilmington, Del.,conductive paint or ink and/or metal films, such as those disclosed inLynam IV. Use of a conductive demarcation means, such as a line of the #7713 silver conductive frit, having a width of about 0.09375″ and athickness of about 50 μm; placed on the conductive surface of one of thesubstrates of the electrochromic device may provide the added benefit ofenhancing electrochromic performance by reducing bus bar-to-bus baroverall resistance and thus enhancing uniformity of coloration, as wellas rapidity of response, particularly over large area devices.

Fabrication of electrochromic multi-radius/aspheric or spherical/convexmirrors can benefit from single or tandem bending such as is describedin U.S. patent application Ser. No. 08/429,643, now U.S. Pat. No.5,724,187, the disclosure of which is hereby incorporated by referenceherein. Convex or multi-radius minilites/shapes can, for example, beindividually bent [and thereafter ITO coated or metal reflector coated(such as with a chromium metal reflector, a chromium undercoat, rhodiumovercoat metal reflector, a chromium undercoat/aluminum overcoatreflector, or their like, such as is described in U.S. patentapplication Ser. No. 08/429,643, now U.S. Pat. No. 5,724,187, and thenthe individual bent minilites/shapes can be selectively sorted so thatthe best matched pairs from a production batch can be selected. Forexample, bent convex or aspheric minilites/shapes can be bent inproduction lots such as of 100 pieces or thereabouts. Thereafter, eachindividual bent minilite/shape is placed in a vision system where thereflection of a pattern of dots, squares, lines, circles, ovals (or thelike) is photographed using a digital camera and the position ofindividual dots, etc., in the pattern, as reflected off the individualminilite/shape being measured, is captured and stored digitally in acomputer storage. Each individual minilite/shape, in turn, is similarlymeasured and a digital image of the reflected image of each part'spattern is also computer stored. An identifier is allocated to eachminilite/shape and to its corresponding computer stored record of thereflected image of the pattern. Next, a computer program finds whichcombination of two minilites/shapes have most closely matched reflectedimages of the fixed pattern (which typically is a dot matrix or thelike). This is achieved, for example, by finding how close the center ofone reflected dot on a given part is located apart from itscorresponding dot on another part. For perfectly matched parts,corresponding dots coincide; when they are located apart, then a localmismatch is occurring. Thus, by using a dot matrix of, for example, 10to 100 dots reflected off a given part, and forming the sum of thesquares of the absolute inter-dot distances to give a figure of meritfor each putative from match, then minilites/shapes can be selectivelysorted by selecting the matched pairs with the lowest inter-dotdistances as indicated by the smallest figure of merit. Alternately, apattern with a measured, pre-established distortion can be designed suchthat, upon reflection off the convex (or concave) surface of a bentminilite/shape, the pattern is reflected as straight, parallel lines.The equipment suitable to use in a vision system is conventional in themachine vision art and includes a digital camera (such as a chargecoupled device (CCD) camera or a video microchip camera (CMOS camera)),a frame grabber/video computer interface, and a computer. Typically thecamera is mounted above (typically 1 foot to 4 feet above, or evenfarther above) the subject minilite/shape, and the camera views throughthe pattern (that typically is an illuminated light box with the patternincorporated therein) to view the pattern's reflection off the convex(or, if desired, the concave) surface of the bent part. If desired,optical calculations can be made that allow determination of the actualprofile of the bent glass based upon measurements taken and calculatedfrom the pattern's reflection.

Also, an aspheric electrochromic (or a convex electrochromic) mirror canbe used as an interior rearview mirror, and can be packaged as a clip-onto an existing vehicular rearview mirror in a manner that is similar toaftermarket wide angle mirrors conventionally known. Such interioraspheric/convex electrochromic mirrors can optionally be solar poweredor be powered by a battery pack, for ease of installation in thevehicular aftermarket. Should it be desirable to minimize weight forconvex or aspheric inside or outside mirrors, then thin glass (in thethickness range of about 1 mm to about 1.8 mm, or even thinner) can beused for one or both of the substrates used in a laminate electrochromicassembly. Use of such thin glass is described in U.S. patent applicationSer. No. 08/429,643 filed Apr. 27, 1995, now U.S. Pat. No. 5,724,187,the disclosure of which is hereby incorporated by reference herein.Also, cutting of convex and especially aspheric glass can benefit fromcomputer numerical controlled (CNC) cutting where a cutting head ismoved under digital computer control. In this regard, a multi-axis CNCcutter is preferred where the cutting head (which may be a diamond toolor wheel, a laser beam, a water jet, an abrasive water jet, or the like)can be moved in three dimensions. Most preferably, and especially forcutting aspheric bent glass, a cutter that moves in three dimensions butthat keeps the cutting tool (such as a diamond wheel) normal (i.e., witha cutting wheel axis at or close to 90° to the tangential plane of thebent glass surface) is preferred. For example, a cutting machine such asavailable from LASER Maschlnenbau GmbH & Company KG, Grossbetlingen,Germany can be used to cut aspheric glass. In such a system, the bentglass lite/minilite from which the shape is to be cut is mounted on asupport arm that is movable in three dimensions and that generally movesin three-dimensions either CNC driven, or by following a cam, along thethree-dimensional profile of the aspheric shape being cut. Also, thecutting wheel can be adjusted so that its angle relative to a tangent tothe glass at point of cut is close to 90° (and not less than about 70°;not less than about 80° more preferred and not less than about 85° mostpreferred). In this manner, movement of the cutting support under thecutting wheel, in combination with adjustment of the pitch of thecutting wheel itself, maintains as close to normal (i.e., 90°) thecutting angle as possible, and thus achievement of a clean, efficientcut and breakout of the shape. While particularly beneficial foraspheric shapes where the radius can change from about 2000 mm to below600 mm, and smaller, across the surface of the shape, cutting of convexglass can also benefit from maintenance of a near normal cutting anglefor the cutting tool (i.e., cutting wheel).

Optionally, a machine vision system can be utilized to determine thesurface profile of the glass to be cut and the data as to the profile isfed back to the cutter's CNC controller to properly orientate the glassunder the cutting head. Use of a vision system, such as is describedabove, to scan and measure the system profile of the glass to be cut canbe thus used to determine how much offset there is on the radius of theglass relative to the cutting head. CNC controlled sensors can beautomatically adjusted on every cutting cycle based on the informationreceived from the vision system. A five-axis shape cutter that allowsthe cutting head to remain approximately perpendicular to the surface ofthe glass regardless of the radius of curvature is commerciallyavailable, such as from LASER Maschlnenbau GmbH & Company KG,Grossbetlingen, Germany. Also, if desired and particularly for thinglass substrates, the front substrate and/or rear substrate can betoughened or tempered (such as by, for example, chemical tempering orcontact tempering) such as described in U.S. Pat. No. 5,239,405 entitled“Near-Infrared Reflecting, Ultraviolet Protected, Safety ProtectedVehicular Glazing” invented by N. Lynam and issued Aug. 24, 1993, thedisclosure of which is hereby incorporated by reference herein. Also, anexterior mirror of this invention can be attached to the backplatecommonly used to mount to the actuator used in an exterior completemirror assembly (as is commonly known in automotive mirror art) by useof a double-sticky tape such as is described in U.S. Pat. No. 5,572,384(see supra) or can be attached using a hot melt adhesive that is appliedto the rearmost surface of the laminate glass assembly (i.e., the rearsurface of the rear glass substrate, often referred to as the fourthsurface of the laminate assembly). Preferably, such hot melt adhesive,when cured, is flexible, provides an anti-scatter function meetingautomotive safety specification and most preferably, is electricallyconductive (such as by inclusion of conductive carbon or conductivemetal flakes or fibrils, such as copper, brass, aluminum or steelfibrils). Also, a heater can be attached to the rearmost surface of thelaminate construction formed by sandwiching the electrochromic mediumbetween the first and second (i.e., front and rear) substrates of anelectrochromic rearview mirror device. Such heater can be directlyapplied to the rearmost glass surface, or can be a separate heater pad,such as is disclosed in U.S. patent application Ser. No. 08/429,643filed Apr. 27, 1995, now U.S. Pat. No. 5,724,187, the disclosure ofwhich is hereby: incorporated by reference herein. Preferably, theheater is combined with the mirror reflector mounting plate (also knownin the automotive mirror art as the mirror backing plate or the mirrorbackplate). More preferably, the heater and/or the mirror backing plateis formed (such as by injection molding, extrusion and the like) of aconductive polymer material such as a polymer resin incorporatingconductive carbon or conductive metal flakes or fibrils (such as ofcopper, brass, aluminum, steel or equivalent metal). Most preferably,the heater and the mirror backing plate are formed and attached to themirror element in an integral molding operation as follows. The mirrorreflector glass (that preferably is an electrochromic mirror cell butthat, optionally, can be a conventional mirror reflector such as chromedglass) is placed in a mold. A heater (such as a positive temperaturecoefficient heater pad, or a pad formed from a conductive polymer resinthat incorporates metal or carbon conducting particles, or a pad formedfrom a resin that is intrinsically self-conducting in its resinstructure such as a polyaniline resin), is either injection molded ontothe rearmost glass surface of the glass reflector element (optionally,with an adhesion promoting primer already applied to the rearmost glasssurface and/or with a heat transfer agent applied to the rearmost glasssurface), or is attached to the rearmost glass surface (or is alreadypre-attached to the rearmost glass surface) using a double-sticky tapeor a hot melt adhesive (preferably, also conducting and/or of high heattransfer efficiency such as aluminum foil). Finally, a plastic resin isinjection molded to form the mirror backing plate (and, optionally, thebezel around the outer perimeter of an electrochromic sideview mirrorsub-assembly as is commonly known in the electrochromic rearview mirrorart). The backing plate for the mirror element is the means forattachment to the electrical or manually operated actuator within thecomplete outside sideview mirror assembly that enables the driver tochange the orientation of the mirror reflector when mounted on thevehicle and to select the mirror's alignment relative to the driver andthus select the rearward view that suits that particular driver's needsfor field of view rearward. By integral molding, the conventionallyseparate steps of separately attaching a heater pad to the mirror glassand then attaching a separately formed backing plate can be reduced to asingle integral molding step where components, including the mirrorglass, are loaded into a mold, plastic resin is injected or plasticresins are co-injected, and a complete sub-assembly (including heater,connectors, bus bars, wire leads/wire harnesses, heat distributors,thermistors, thermal cut-off switches, backing plate, bezel, etc.) isunloaded from the tool after completion of the integral molding step.

Further, vehicle warning indicia such as the familiar “OBJECTS MAY BECLOSER THAN THEY APPEAR” can be created (such as by silk-screening,dispensing, printing, etc.) using a conductive material (such as aconductive ink, conductive paint, conductive polymer and the like). Inthis way, electrical conductivity is maintained across the full surfaceof the inward facing surface of the rear substrate (frequently calledthe third surface). Where a metal reflector (such as a chromium layer oran underlayer of chromium overcoated with a higher reflecting metallayer such as of silver, aluminum or rhodium) is used as a third surfacereflector, the metal reflector can first be deposited (such as bysputter deposition utilizing planar magnetron or rotary magnetroncathodes) onto the conductive surface of TEC glass (or any othertransparent conductive coated surface). Next, the metal reflector can beselectively removed to form the desired indicia (i.e., a “HEATED”symbol, a manufacturer's date code and ID, a hazard warning indicia suchis commonly found on signal mirrors such as are available on MY97 FordBronco and Ford Expedition vehicles available from Ford Motor Company,Detroit, Mich. and as described in U.S. Pat. No. 5,207,492 invented byRoberts and issued May 1993, the disclosure of which is herebyincorporated by reference herein). The metal reflector can be removedusing chemical etching through a mask or directly using laser scribing(such as with a YAG laser), by controlled sandblasting, and the like. Byselectively removing the overlayering metal reflector but leaving theunderlying transparent conductor largely intact, electrical conductivityacross the third surface (i.e., the inward facing surface of the rearsubstrate) is largely undistributed, and electrochromic coloration iscorrespondingly uniform. Should it be desired to read an indicia on athird surface, then backlighting can be provided on the fourth surface(i.e., the non-inward facing surface of the rear substrate) that can beviewed by reading through the indicia created on the third surface byremoving a third surface metal reflector. Also, optionally, a conductiveindicia of a non-dark color (such as brilliant white) could be createdon the surface (i.e., the inward facing surface of the front substrate)of the laminate electrochromic assembly. Thus, when the electrochromicmedium colors, the indicia remains visible as a color contrast againstthe colored dimmed state of the electrochromic medium. Preferably, andas stated above, the indicia is created from conducting or at leastpartially conducting material (such as can be achieved using conductivecarbon fillers). Alternately, non-conducting non-dark colored indiciacan be used on the second surface of the laminate assembly. Preferably,such non-dark colored indicia are bright and somewhat reflecting so thatthey maintain good color contrast in the dimmed state of theelectrochromic mirror.

Once constructed, any of the electrochromic devices described herein mayhave a molded casing placed therearound. This molded casing may bepre-formed and then placed about the periphery of the assembly or, forthat matter, injection molded therearound using conventional techniques,including injection molding of thermoplastic materials, such aspolyvinyl chloride [see e.g., U.S. Pat. No. 4,139,234 (Morgan)], orreaction injection molding of thermosetting materials, such aspolyurethane or other thermosets [see e.g., U.S. Pat. No. 4,561,625(Weaver)]. Thus, modular automotive glazings incorporating polychromicsolid films may be manufactured.

Also, optionally and preferably when a thin glass (less than 0.191 cm)front (first) substrate is used in an automotive mirror, the frontsubstrate 2 that would first be impacted by an impinging object can betoughened and/or tempered such as is disclosed in U.S. Pat. No.5,115,346 and U.S. patent application Ser. No. 08/866,764 filed May 30,1997 to a “Method and Apparatus for Tempering and Bending Glass”, nowU.S. Pat. No. 5,938,810, the disclosures of which are herebyincorporated by reference herein. Such toughening/tempering can beachieved by chemical tempering/strengthening, by air tempering, bycontact tempering or by bladder bending/tempering as disclosed in the'764 application above.

Polychromic solid films may be used in a variety of automotive rearviewmirror assemblies including those assemblies described in U.S. patentapplication Ser. No. 08/799,734 entitled “Vehicle Blind Spot DetectionDisplay System”, invented by Schofield et al. and filed Feb. 12, 1997,now U.S. Pat. No. 5,786,772, the disclosure of which is herebyincorporated herein by reference.

As disclosed in the U.S. patent application Ser. No. 08/799,734 (nowU.S. Pat. No. 5,786,772), a vehicle 10 includes an interior rearviewmirror 12 positioned within passenger compartment 13 of vehicle 10, adriver's side exterior rearview mirror 14 and a passenger's sideexterior rearview mirror 16 (FIG. 3). Vehicle 10 further includes ablind spot detection system 18 made up of a blind spot detector 20 and ablind spot detection display system 22 (FIG. 4). The blind spot detectormay be an infrared blind spot detection system of the type disclosed inU.S. provisional application Ser. No. 60/013,941, filed Mar. 22, 1996,by Kenneth Schofield entitled PROXIMITY DETECTION OF OBJECTS IN ANDAROUND A VEHICLE, the disclosure of which is hereby incorporated byreference, or International Patent Application No. WO 9525322 A1,published Sep. 21, 1995, by Patchell et al., entitled VEHICLE-MOUNTEDDETECTOR TO SENSE MOVING VEHICLE IN BLIND SPOT; an optical blind spotdetection system of the type disclosed in U.S. Pat. No. 5,424,952(Asayama); a radar-based blind spot detection system of the typedisclosed in U.S. Pat. No. 5,325,096 (Pakett); an ultrasonic blind spotdetection system of the type disclosed in U.S. Pat. No. 4,694,295(Miller et al.); or any other of the known types of blind spot detectionsystems. As is common, blind spot detector 20 may be incorporated inexterior mirrors 14, 16, but may, alternatively, be independentlypositioned on the side of the vehicle being protected by the blind spotdetector, as is known in the art. Blind spot detector 20 may include aseparate control 24 or may incorporate the control function in the samehousing with the blind spot detector 20.

Blind spot detection display system 22 includes a first indicatorassembly 26 positioned on vehicle 10 in the vicinity of driver's sideexterior mirror 14. First indicator assembly 26 includes a firstindicator 28 to produce a visual indication to the driver of thepresence of an object, such as an overtaking vehicle, adjacent thedriver's side of the vehicle. First indicator assembly 26 may includesecond indicator 30 that the blind spot detector is operational. Firstindicator assembly 26 may additionally include a third indicator 32which provides an indication that an object in the blind spot on thedriver's side of the vehicle is receding from that blind spot. In orderto provide additional visual clues to the driver of the meaning of eachof the indicators, the first indicator 28 is most preferably a redindicator, the second indicator 30 is a green indicator and thirdindicator 32 is an amber indicator. In the illustrated embodiment, firstindicator assembly 26 is positioned on passenger's side exterior mirror14 and, more specifically, includes a plurality of LED indicatorspositioned behind the reflective element 34 of the exterior mirror.Alternatively, the first indicator assembly 26 may be positioned on theface of housing 36 for reflective element 34. Alternatively, firstindicator assembly 26 may be positioned in the pillar (not shown)located on the driver's side of the vehicle. Although not on thedriver's side exterior mirror, such location on the pillar is adjacenton the driver's side exterior mirror.

Blind spot detection display system 22 includes a second indicatorassembly 38 positioned on interior mirror assembly 12. Second indicatorassembly 38 includes a first indicator 40 to provide an indication ofthe presence of an object adjacent the driver's side of the vehicle. Assuch, first indicator 40 is illuminated concurrently with firstindicator 28 of first indicator assembly 26. Although not shown, secondindicator assembly 38 may, optionally, include second and thirdindicators which are illuminated concurrently with second and thirdindicators 30, 32 of first indicator assembly 26. Preferably, only asingle indicator is provided in order to provide an awareness to thedriver of the primary indication produced by a blind spot detector;namely, the presence of a vehicle adjacent the associated side of thevehicle. In order to increase the cognitive association by the driverbetween the indication and the event being indicated, second indicatorassembly 38 is positioned at a portion 42 of interior mirror 12 which istoward the driver's side of vehicle 10.

In a second embodiment, as illustrated in FIG. 5, a blind spot detectionsystem 18′ includes a first blind spot detector 20 a detecting thepresence of objects in the blind spot on the driver's side of thevehicle and a second blind spot detector 20 b detecting the presence ofobjects in the blind spot on the passenger's side of the vehicle. Blindspot detection system 18′ includes a blind spot detection display system22′ which includes a third indicator assembly 44 positioned on vehicle10 adjacent passenger's side exterior mirror 16. Blind spot detectiondisplay system 22′ additionally includes a fourth indicator assembly 46on interior mirror assembly 12. Both the third and fourth indicatorassemblies are adapted to producing an indication at least of thepresence of an object adjacent the passenger's side of vehicle 1O.fourth indicator assembly 46 includes a first indicator 48 which isilluminated concurrently with a first indicator 28′ of third indicatorassembly 44. Third indicator assembly 44 may include a second indicator30′ to indicate that blind spot detector 20 b is operational. In theillustrated embodiment, blind spot detection system 18′ does not includean indication of the presence of a vehicle in the blind spot that isreceding from the respective side of the vehicle. However, such thirdindicator may optionally be provided. First indicator 48 of fourthindicator assembly 46 is positioned at a portion 50 of exterior mirror12 which is toward the passenger's side of the vehicle. In this manner,additional cognitive association is provided for the purpose ofassociation by the driver between the indication and the event beingindicated.

In use, first and second indicator assemblies 26, 38 will provide anindication to the driver of the presence of a vehicle, or other object,in the driver's blind spot on the driver's side of the vehicle and thirdand fourth indicator assemblies 44, 46 will provide an indication to thedriver of the presence of a vehicle, or other object, in the driver'sblind spot on the passenger's side of the vehicle. When the driverperforms a premaneuver evaluation, the driver is immediately apprised ofthe presence of a vehicle on the passenger's and/or driver's side of thevehicle upon the driver's viewing of the interior rearview mirror 12,which research indicates is the first step taken by most drivers ininitiating the premaneuver evaluation prior to making a lane change orthe like. During subsequent portions of the premaneuver evaluation, thedriver may initially be apprised of the presence of a vehicle in thedriver's side blind spot by first indicator assembly 26 or in thepassenger's side blind spot by the third indicator assembly 44 whenviewing the respective exterior mirror assembly 14, 16. Thus, it is seenthat a natural and intuitive blind spot detection display system isprovided. Blind spot detection display system 22, 22′ not only providesindications to the driver of the presence of a vehicle in a blind spotduring more portions of the premaneuver evaluation, but additionallyprovides indications to the driver should dew, frost, or road dirt maskthe indication associated with the exterior rearview mirrors.

Control 24, 24′ may modulate the intensity of the indication provided bythe first, second, third and fourth indicator assemblies primarily as afunction of light levels surrounding vehicle 10. This may be in responseto light levels sensed by light sensors (not shown) associated with adrive circuit (not shown) for establishing the partial reflectance levelof interior rearview mirrors 12 and/or exterior rearview mirrors 14, 16or may be a separate light sensor provided for the purpose ofestablishing an input to control 24, 24′.

In the illustrative embodiment, interior rearview mirror 12 includes areflective element 52 and a housing 54 for reflective element 52. Secondand fourth indicator assemblies 38, 46 may be positioned on reflectiveelement 52 and provide a through-the-cell display such as of the typedisclosed in U.S. Pat. No. 5,285,060 issued to Mark L. Larson et al. fora DISPLAY FOR AUTOMATIC REARVIEW MIRROR, the disclosure of which ishereby incorporated herein by reference. In particular, if the indicatorassembly is behind a variable reflective element, the intensity of theindicator assembly is adjusted as a function of the reflectance level ofthe variable reflective element as disclosed in the '060 patent.

In an alternative embodiment, a blind spot detection system 18″ includesan exterior mirror 14′ having a reflective element 34′ and a housing 36′for the reflective element (FIG. 6). A first indicator assembly 26′ iscomposed of a sealed module mounted to housing 36′ in a manner whichcompletes the overall slope of the exterior mirror. Such module isgenerally constructed according to the principles described in U.S. Pat.No. 5,497,306 issued to Todd W. Pastrick for an EXTERIOR VEHICLESECURITY LIGHT, the disclosure of which is incorporated herein byreference. First indicator assembly 26′ includes a module 56 made up ofa case 55 having an opening 58 and an optionally transmitting cover orlens 68 closing the opening in a manner which provides a sealedenclosure. A lamp assembly 60 is positioned within opening 58 andincludes a plurality of indicators, such as light-emitting diodes (LEDs)62 physically supported by and electrically actuated through a printedcircuit board 63. A lower assembly 64 provides a plurality of louvers 66which separate the LEDs and direct the light generated by the LEDs inthe direction of a driver seated in vehicle 10.

In operation, the plurality of indicators making up indicator assembly26′ are cumulatively progressively energized in a manner which indicatesthat another vehicle is approaching the detected blind spot of vehicle10 and is actually within the blind spot of the vehicle. For example, aprogressively greater number of indicators can be energized as anothervehicle approaches the blind spot of vehicle 10, with the number ofenergized indicators increasing as the other vehicle gets closer to theblind spot of vehicle 10. When the other vehicle is actually within theblind spot of vehicle 10, all of the indicators would be actuated. Asthe other vehicle moves out of the blind spot of vehicle 10, the numberof energized indicators will decrease the further the other vehiclemoves from the blind spot.

The indicator assemblies may perform multiple display functions such asproviding indication of an additional vehicle function, such as acompass mirror display function, a temperature display function, apassenger air bag disable display function, an automatic rain sensoroperation display function, or the like. Such automatic rain sensoroperation display function may include a display function related toboth a windshield-contacting and a non-windshield-contacting rainsensor, including, for example, where the circuitry to control the rainsensor, electrochromic dimming of a variable reflectance electrochromicmirror, and any other mirror-mounted electronic feature are commonlyhoused in a rearview mirror assembly and wholly or partially sharecomponents on a common circuit board. The blind spot detection displayor the automatic rain sensor operation display may alternate with theother display function by a display toggle which may be manuallyoperated, time-shared, voice-actuated, or under the control of someother sensed function, such as a change in direction of the vehicle orthe like. For example, if the through-the-cell display described in theLarson et al. '060 patent is used, it would be desirable to minimize thesize of the display because the display generally takes away from theviewing area of the mirror. Multiple parameters, such as temperature,vehicle heading, and one or more icons, can all be indicated withoutincreasing the size of the display by, for example, having the one ormore icons coming on for a particular interval followed by display ofthe temperature and vehicle heading. For example, the temperature andheading displays can be time-shared by alternatingly displayingtemperature and heading with the cycle of alternation selected from arange of from approximately one (1) second to approximately 25 seconds.Alternatively, the driver can be provided with an input reflectiveelement, such as a switch, to allow the driver to choose which parameterto display. In yet an additional alternative, one of the parameters canbe normally displayed with the driver being provided with an overridefunction to allow display of the other parameter. Other variations willbe apparent to those skilled in the art.

Also, they may be used in association with rain sensor interior mirrorassemblies wherein a rain sensor functionality, as is commonly known inthe automotive art, is provided in association with an interior rearviewmirror assembly. Such association includes utilizing an element of therearview mirror assembly (such as a plastic housing attached, forexample, to the mirror channel mount that conventionally attaches themirror assembly to a windshield button slug) to cover awindshield-contacting rain sensor (such as is described in U.S. Pat. No.4,973,844 titled “Vehicular Moisture Sensor and Mounting ApparatusTherefor”, invented by O'Farrell et al. and issued Nov. 27, 1990, thedisclosure of which is hereby incorporated herein by reference), or itmay include a non-windshield-contacting rain sensor (such as isdescribed in PCT International Application. PCT/US94/05093 entitled“Multi-Function Light Sensor for Vehicle” invented by Dennis J. Hegyl,published as WO 94/27262 on Nov. 24, 1994, the disclosure of which ishereby incorporated by reference herein). The rearview mirror assemblycan include a display function (or multiple display functions).

These displays may perform a single display function or multiple displayfunctions such as providing indication of an additional vehiclefunction, such as a compass mirror display function, a temperaturedisplay function, status of inflation of tires display function, apassenger air bag disable display function, an automatic rain sensoroperation display function, telephone dial information display function,highway status information display function, blind spot indicatordisplay function, or the like. Such display may be an alpha-numericaldisplay or a multi-pixel display, and maybe fixed or scrolling. Such anautomatic rain sensor operation display function may include a displayfunction related to both a windshield-contacting and anon-windshield-contacting rain sensor, including, for example, where thecircuitry to control the rain sensor, electrochromic dimming of avariable reflectance electrochromic mirror, and any other mirror-mountedelectronic feature are commonly housed in or on a rearview mirrorassembly and wholly or partially share components on a common circuitboard. The blind spot detection display or the automatic rain sensoroperation display may alternate with other display functions by adisplay toggle which may be manually operated, time-shared,voice-actuated, or under the control of some other sensed function, suchas a change in direction of the vehicle or the like. Should a rainsensor control be associated with, incorporated in, or coupled to theinterior rearview mirror assembly, the rain sensor circuitry, inaddition to, providing automatic or semi-automatic control overoperation of the windshield wipers (on the front and/or rear windshieldof the vehicle), can control the defogger function to defog condensedvapor on an inner cabin surface of a vehicle glazing (such as the insidesurface of the front windshield, such as by operating a blower fan,heater function, air conditioning function, or their like), or the rainsensor control can close a sunroof or any other movable glazing shouldrain conditions be detected. As stated above, it may be advantageous forthe rain sensor control (or any other feature such as a head-lampcontroller, a remote keyless entry receiver, a cellular phone includingits microphone, a vehicle status indicator and the like) to sharecomponents and circuitry with the electrochromic mirror function controlcircuitry and electrochromic mirror assembly itself. Also, a convenientway to mount a non-windshield-contacting rain sensor such as describedby Hegyl is by attachment, such as by snap-on attachment, as a module tothe mirror channel mount such as is described in U.S. Pat. No. 5,576,678entitled “Mirror Support Bracket,” invented by R. Hook et al. and issuedNov. 19, 1996, the disclosure of which is hereby incorporated byreference herein. The mirror mount and/or windshield button mayoptionally be specially adapted to accommodate a non-windshield mountingrain sensor module. Such mounting as a module is readily serviceable andattachable to a wide variety of interior mirror assemblies (bothelectrochromic and non-electrochromic such as prismatic, manuallyadjusted mirror assemblies), and can help ensure appropriate alignmentof the non-windshield-mounted variety of rain sensor to the vehiclewindshield insofar that the module attached to the mirror mount remainsfixed whereas the mirror itself (which typically attaches to the mirrorchannel mount via a single or double ball joint) is movable so that thedriver can adjust its field of view. Also, should smoke from cigarettesand the like be a potential source of interference to the operation ofthe non-windshield-contacting rain sensor, then a mirror-attachedhousing can be used to shroud the rain sensor unit and shield it fromsmoke (and other debris). Optionally, such ability to detect presence ofcigarette smoke can be used to enforce a non-smoking ban in vehicles,such as is commonly requested by rental car fleet operators. Also, whena rain sensor (contacting or non-contacting) is used to activate thewiper on the rear window (rear backlight) of the vehicle, the sensor canbe conveniently packaged and mounted with the CHMSL (center high mountedstop light) stop light assembly commonly mounted on the rear windowglass or close to it. Mounting of the rain sensor with the CHMSL stoplight can be aesthetically appealing and allow sharing ofcomponents/wiring/circuitry.

The electrochromic solid films can be used with interior rearviewmirrors equipped with a variety of features such as a control toopen/close a gasoline fill cap or a rear tank or a front bonnet, ahigh/low (or daylight running beam/low) headlamp controller,altitude/incline display, a hands-free phone attachment, a video camerafor internal cabin surveillance and/or video telephone function, avehicle mounted remote transaction interface system (such as would allowpayment for gas purchases, automatic bank teller interactions, etc.)seat occupancy detection, map reading lights (including map readinglights comprising an incandescent lamp, an array of light emittingdiodes or a solid state diode laser/array of solid state diode lasers),compass/temperature display, fuel level and other vehicle statusdisplay, a train warning system display, a trip computer, an intrusiondetector and the like. Again, such features can share components andcircuitry with the electrochromic mirror circuitry and assembly so thatprovision of these extra features is economical.

Placement of a video camera either at, within, or on the interiorrearview mirror assembly (including within or on a module attached to amirror structure such as the mount that attaches to the windshieldbutton) has numerous advantages. For example, the mirror is centrallyand high mounted and so is in a location that has an excellent field ofview of the driver, and of the interior cabin in general. Also, it is adefined distance from the driver and so focus of the camera isfacilitated. Also, if placed on the movable portion of the mirrorassembly, the normal alignment of the mirror reflector relative to thedriver's field of vision rearward via the mirror can be used to readilyalign the video camera to view the head of the driver. Since manyinterior rearview mirrors are electrically serviced, placement of acamera at within, or on the rearview mirror assembly can be convenientlyand economically realized, with common sharing of components andcircuitry by, for example, a compass direction function (which mayinclude a flux gate sensor, a magneto-resistive sensor, amagneto-inductive sensor, or a magneto-capacitive sensor), an externaltemperature display function and the electrochromic dimming function.Although the driver is likely the principal target and beneficiary ofthe video camera, the video camera field of view can be mechanically orelectrically (i.e., via a joystick) adjusted to view Otherportions/occupants of the vehicle cabin interior. In this regard, thejoystick controller that adjusts the position of the reflector on theoutside rearview mirrors can, optionally, be used to adjust the videocamera field of view as well. The video camera can be a CCD camera or aCMOS based video microchip such as is described in PCT Application No.94/01954 filed Feb. 25, 1994, the disclosure of which is herebyincorporated by reference herein. For operation at night, the internalcabin of the vehicle may optionally be illuminated with non-visibleradiation, such as near-infrared radiation, and the video camera can beresponsive to said near-infrared radiation so that a video telephonecall can be conducted even when the interior cabin is dark to visiblelight, such as at night. Also, the video camera mounted at, within or onthe inner rearview mirror assembly (such as within the mirror housing orin a pod attached to the mirror mount) can be utilized to capture animage of the face of a potential driver and then, using appropriateimage recognition software, decide whether the driver is authorized tooperate the vehicle and, only then, enable the ignition system to allowthe motor of the vehicle be started. Use of such a mirror-mounted videocamera (or a digital still camera) enhances vehicle security and reducestheft. Further, the video camera can monitor the driver while he/she isdriving and, by detection of head droop, eye closure, eye pupil change,or the like, determine whether the driver is becoming drowsy/fallingasleep, and then activate a warning to the driver to stay alert/wake up.It is beneficial to use a microprocessor to control multiple functionswithin the interior mirror assembly and/or within other areas of thevehicle (such as the header console area), and such as is described inIrish Patent Application No. 970014 entitled “A Vehicle Rearview Mirrorand A Vehicle Control System Incorporating Such Mirror,” applicationdate Jan. 9, 1997, the disclosure of which is hereby incorporated byreference herein. Such microprocessor can, for example, control theelectrochromic dimming function, a compass direction display and anexternal temperature display. For example, a user actuatable switch canbe provided that at one push turns on a compass/temperature display, onsecond push changes the temperature display to metric units (i.e., todegrees Celsius), on third push changes to Imperial units (i.e., degreesFahrenheit) and on fourth push turns off the compass/temperaturedisplay, with the microprocessor controlling the logic of the display.Alternately, a single switch actuation turns on the display in Imperialunits, the second actuation changes it to metric units, and thirdactuation turns the display off. Further, the displays and functionsdescribed herein can find utility also on outside rearview mirrors. Forexample, a transducer that receives and/or transmits information to acomponent of an intelligent highway system (such as is known in theautomotive art) can be incorporated into an interior and/or outsiderearview mirror assembly. Thus, for example, a transmitter/receiver forautomatic toll booth function could be mounted at/within/on an outsidesideview mirror assembly. A digital display of the toll boothtransaction can be displayed by a display incorporated in the interiorrearview mirror assembly. Optionally, a micro printer incorporatedwithin the rearview mirror can print a receipt of the transaction.Similarly, for safety and security on the highways, GPS information,state of traffic information, weather information, telephone numberinformation, and the like may be displayed and transmitted/received viatransducers located at, within, or on an interior rearview mirrorassembly and/or an outside sideview mirror assembly. Also, the interiorrearview mirror assembly can include a link to the Worldwide Web via theINTERNET. Such as via a modem/cellular phone mounted within the vehicle,and preferably, mounted at, within or on the interior rearview mirrorassembly. Thus, the driver can interact with other road users, canreceive/transmit messages including E-mail, can receive weather andstatus of highway traffic/conditions, and the like, via a mirror locatedinterface to the INTERNET.

Further, a trainable garage door opener such as a universal garage dooropener such as is available from Prince Corporation, Holland, Mich.under the tradename HOMELINK™, or the transmitter for a universal homeaccess system that replaces the switch in a household garage thatopens/closes the garage door with a smart switch that is programmable toa household specific code that is of the rolling code type, such as isavailable from TRW Automotive, Farmington Hills, Mich. under thetradename KWIKLINK™ may be mounted at, within, or on the interior mirror(or, if desired, the outside sideview mirror). Switches to operate suchdevices (typically up to three separate push type switches, each for adifferent garage door/security gate/household door) can be mounted onthe mirror assembly, preferably user actuatable from the front face ofthe mirror housing. Preferably, the universal garage door openerHOMELINK™ unit or the universal home access KWIKLINK™ unit is mountedat, within or on the interior rearview mirror assembly. Optionally, sucha unit could be mounted at, within or on an outside sideview mirrorassembly.

The KWIKLINK™ Universal Home Access System (which operates on a rollingcode, such as is commonly known in the home/vehicle security art)comprises a vehicle mounted transmitter and a receiver located in thegarage. The KWIKLINK™ system is a low-current device that can be,optionally, operated off a battery source, such as a long life lithiumbattery. It is also compact and lightweight as executed on a single- ordouble-sided printed circuit board. The KWIKLINK™ printed circuit boardcan be mounted within the mirror housing (optionally adhered to a shockabsorber comprising a double-sticky tape anti-scatter layer on the rearof the reflector element (prismatic or electrochromic) such as isdescribed in U.S. Pat. No. 5,572,354 entitled “Rear Mirror Assembly”,invented by J. Desmond et al. and issued Nov. 5, 1996, the disclosure ofwhich is hereby incorporated by reference herein or may be accommodatedwithin a detachable module, such as the pod described in U.S. Pat. No.5,576,678 entitled “Mirror Support Bracket”, invented by R. Hook et al.and issued Nov. 19, 1996, the disclosure of which is hereby incorporatedby reference herein, and with the detachable module attached to themirror mount or to the mirror button. Mounting the KWIKLINK™ unit in adetachable module has advantages, particularly for aftermarket supplywhere a battery operated KWIKLINK™ unit can be supplied within a podhousing (with the necessary user actuatable button or buttons mounted onthe pod and with the battery being readily serviceable either by accessthrough a trap door and/or by detaching the pad from the mirror mount).By supplying a battery-operated, stand-alone, snap-on, detachableKWIKLINK™ mirror mount pod, the KWIKLINK™ home access system can bereadily and economically provided to a broad range of mirrors (includingnon-electrical mirrors such as base prismatic mirrors, and electricalmirrors such as lighted prismatic mirrors and electo-optic mirrors, suchas electrochromic mirrors). Further, a solar panel can be installed onthe pod housing to recharge the battery.

Also, the pod module assembly may have a windshield button mountattached thereto or incorporated therein and have, in addition, astructure that replicates the windshield button standard on mostvehicles manufactured in the United States. Thus, when a consumerpurchases such an aftermarket product, the consumer simply removes theexisting interior rearview mirror assembly from the windshield button itis attached to in the vehicle. Then, the consumer attaches the podmodule windshield button mount to the windshield button attached to thewindshield (this can be achieved either by sliding on and securing witha screwdriver, or by snap-on in a manner conventional in the mirrormounting art). Finally, the consumer now attaches the rearview mirrorassembly to the windshield button replication structure that is part ofthe aftermarket pod module. Since the windshield button shape is largelyan industry standard (but the interior rearview mirror mount thatattaches thereto is typically not standard), by using this “button on abutton” pod module design, an aftermarket product (such as a pod moduleincorporating a home access transmitter, a universal garage door opener,a security monitor such as a pyroelectric intrusion detector (such asdisclosed in U.S. patent application Ser. No. 08/720,237 filed Sep. 26,1996, the disclosure of which is hereby incorporated by referenceherein), a remote keyless entry receiver, a compass, a temperatureand/or clock function and the like) may be readily installed by thevehicle owner, and the existing rearview minor assembly can be readilyremounted in the vehicle.

Also, a cellular phone can be incorporated into the interior mirrorassembly with its antenna, optionally, incorporated into the outsidesideview mirror assembly or into the inside rearview mirror assembly.Such mounting within the mirror assemblies has several advantagesincluding that of largely hiding the cellular phone and antenna fromready view by a potential thief. Further, a seat occupancy detectorcoupled to an air bag deployment/disable monitor can be located at,within or on the interior rearview mirror assembly. The seat occupancydetector can be a video microchip or CD camera seat occupancy detector,an ultrasonic detector or a pyroelectric detector, or their combination.Moreover, where more than one rearview mirror is being controlled oroperated; or when several vehicle accessories are linked to, forexample, an electrochromic interior or outside mirror, interconnectionscan be multiplexed, as is commonly known in the automotive art.Moreover, where it is desired to display external outdoor temperaturewithin the interior cabin of the vehicle, a temperature sensor (such asa thermocouple or thermistor) can be mounted at, within or on an outsidesideview mirror assembly (for example, it can protrude into theslipstream below the lower portion of the sideview mirror housing in amanner that is aesthetically and styling acceptable to the automakersand to the consumer) and with the temperature sensor output connected,directly or by multiplexing to a display (such as a vacuum fluorescentdisplay) located in the interior cabin of the vehicle.

Preferably, the external temperature display is located at, within or onthe interior rearview mirror assembly, optionally in combination withanother display function such as a compass display (see U.S. patentapplication Ser. No. 08/799,734, entitled “Vehicle Blind Spot DetectionSystem” invented by K. Schofield et al., and filed Feb. 12, 1997, nowU.S. Pat. No. 5,786,772), or as a stand-alone pod attached as a moduleto a mirror support supper member (see U.S. Pat. No. 5,576,687). Mostpreferably, the interior and outside mirror assemblies are supplied bythe same supplier, using just-in-time sequencing methods, such as iscommonly known in the automotive supply art and as is commonly used suchas for supply of seats to vehicles. Just-in-time and/or sequencingtechniques can be used to supply a specific option (for example, theoption of configuring an external temperature display with a baseprismatic interior mirror, or with a base electrochromic interiormirror, or with a compass prismatic interior mirror, or with a compasselectrochromic interior mirror) for an individual vehicle as it passesdown the vehicle assembly line. Thus, the automaker can offer a widearray of options to a consumer from an option menu. Should a specificcustomer select an external temperature display for a particular vehicledue to be manufactured by an automaker at a particular location on aspecific day/hour, then the mirror system supplier sends to the vehicleassembly plant, in-sequence and/or just-in-time, a set of an interiorrearview mirror assembly and at least one outside sideview mirrorassembly for that particular vehicle being produced that day on theassembly line, and with the outside sideview mirror equipped with anexternal temperature sensor and with the interior rearview mirrorassembly equipped with an external temperature display. Suchjust-in-time, in-sequence supply (which can be used for theincorporation of the various added features recited supra and below) isfacilitated when the vehicle utilizes a car area network such as isdescribed, in Irish Patent Application No. 970014 entitled “A VehicleRearview Mirror and A Vehicle Control System Incorporating Such Mirror”,application date Jan. 9, 1997, the disclosure of which is herebyincorporated by reference herein, or when multiplexing is used, such asis disclosed in U.S. patent application Ser. No. 08/679,681 entitled“Vehicles Mirror Digital Network and Dynamically Interactive MirrorSystem”, invented by O'Farrell et al., and filed Jul. 11, 1996, now U.S.Pat. No. 5,798,575, the disclosure of which is hereby incorporated byreference herein. Also, given that an interior electrochromic mirror canoptionally be equipped with a myriad of features (such as map lights,reverse inhibit line, headlamp activation, external temperature display,remote keyless entry control, and the like), it is useful to equip suchassemblies with a standard connector (for example, a 10-pin, parallelconnector) so that a common standard wiring harness can be providedacross an automaker's entire product range. Naturally, multiplexingwithin the vehicle can help alleviate the need for more pins on such aconnector, or allow a given pin or set of pins control more than onefunction.

Polychromic solid films can be used in added feature interior rearviewmirror assemblies including those that include a loudspeaker (such asfor a vehicle audio system, radio or the like, or for a cellular phoneincluding a video cellular phone). Such loudspeaker may be a highfrequency speaker that is mounted at, within, or on the interiorrearview mirror assembly (such as within the mirror housing or attachedas a module-type pod to the mirror mount such as is described supra) andwith its audio output, preferably, directed towards the front windshieldof the vehicle so that the windshield itself at least partially reflectsthe audio output of the speaker (that preferably is a tweeter speaker,more preferably is a compact (such as about 1″×1″×1″ in dimensions orsmaller), and most preferably utilizes a neodynium magnet core) backinto the interior cabin of the vehicle. The interior rearview mirrorassembly can also include a microphone and a digital (or a conventionalmagnetic tape) recorder that can be used by vehicle occupants to recordmessages and the like. A display can be provided that receives paginginformation from a pager incorporated in the interior rearview mirrorassembly and that displays messages to the driver (preferably via ascrolling display) or to other occupants. The interior rearview mirrorassembly can include a digital storage of information such as phonenumbers, message reminders, calendar information and the like, that canautomatically, or on demand, display information to the driver.

Each of the documents cited in the present teaching is hereinincorporated by reference to the same extent as if each document hadindividually been incorporated by reference.

In view of the above description of the instant invention, it is evidentthat a wide range of practical opportunities is provided by the teachingherein. The following examples illustrate the benefits and utility ofthe present invention and are provided only for purposes ofillustration, and are not to be construed so as to limit in any way theteaching herein.

EXAMPLES

In each of these examples, we selected random assemblies, fractured thesubstrates of the assemblies and scraped the polychromic solid film thathad formed during the transformation process within the assembly fromthe broken substrate.

Scatter Safety Aspect of Electrochromic

Devices Manufactured with Polychromic Solid Films

To demonstrate the safety performance of the electrochromic devicesmanufactured according to the these examples, we simulated the impact ofan accident by impacting the glass substrates of randomly selecteddevices with a solid object so as to shatter the glass substrates ofthose devices. We observed that in each instance the shattered glass washeld in place by the polychromic solid film such that glass shards fromthe broken substrates did not separate and scatter from the device.

Stability and Cyclability of Electrochromic

Devices Manufactured with Polychromic Solid Films

In general, we observed good cycle stability, heat stability,performance under prolonged coloration and ultraviolet stability of theelectrochromic devices manufactured with the polychromic solid films ofthe present invention.

To demonstrate the cycle stability, ultraviolet stability and thermalstability of some of the electrochromic devices manufactured with thepolychromic solid films of the present invention, we subjectedelectrochromic mirrors to (1) 15 seconds color—15 seconds bleach cyclesat both room temperature and about 50° C.; (2) ultraviolet stabilitytests by exposing the electrochromic mirrors to at least about 900 KJ/m²using a Xenon Weatherometer as per SAE J1960 and (3) thermal stabilitytests at about 85° C.

In these mirrors, we observed no change of electrochromic performance ordegrading of the electrochromic devices after more than about 100,000cycles (15 seconds color—15 seconds bleach) at room temperature and morethan about 85,000 cycles (15 seconds color—15 seconds bleach) at about50° C., and after exposure to about 900 KJ/m² of ultraviolet radiationand to about 85° C. for about 360 hours indicating excellent cyclestability and weatherability.

Example 1

In this example, we chose a RMPT-HVBF₄ electrochromic pair, inconjunction with a commercially available ultraviolet curableformulation, to illustrate the beneficial properties and characteristicsof the polychromic solid films and electrochromic interior automotivemirrors manufactured therewith.

A. Synthesis and Isolation of RMPT

We synthesized 2-methyl-phenothiazine-3-one according to the proceduredescribed in European Patent Publication EP 0 115 394 (Merck FrosstCanada). To reduce MPT to RMPT, we followed the redox proceduredescribed in commonly assigned U.S. patent application Ser. No.07/935,784 (filed Aug. 27, 1992), now U.S. Pat. No. 5,500,760.

B. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.7% HVBF₄ (as a cathodic compound),about 1.6% RMPT (as an anodic compound), both homogeneously dispersed ina combination of about 47.4% propylene carbonate (as the plasticizer)and, as a monomer component, about 52.6% “IMPRUV” (an ultravioletcurable formulation). We thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

C. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HW-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×37 μm, with aweather barrier of an epoxy resin coupled with spacers of about 37 μmalso applied.

We placed into the mirror assemblies the electrochromic monomercomposition of Example 1(B), supra, by the vacuum backfilling technique[as described in Varaprasad III, supra].

D. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 1 (B), supra, wasuniformly applied within the mirror assemblies of Example 1(C), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B. While the belt advanced initially at a rate of abouttwenty-five feet per minute, we exposed the assemblies to ultravioletradiation generated by the D fusion lamp of the F-300 B. We passed theassemblies under the fusion lamp light eight times at that rate, pausingmomentarily between passes to allow the assemblies to cool, then eighttimes at a rate of about fifteen feet per minute again pausingmomentarily between passes to allow the assemblies to coot and finallythree times at a rate of about ten feet per minute with theaforementioned pausing between passes.

E. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a bluish purple color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 71% reflectance which decreased to a lowreflectance of about 10.8% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 3.7 seconds. We madethis determination by following the SAE J964a standard procedure of theSociety of Automotive Engineers, with a reflectometer—set in reflectancemode—equipped with a light source (known in the art as Illuminant A) anda photopic detector assembly interfaced with a data acquisition system.

We also observed that the mirror bleached from about 20% reflectance toabout 60% reflectance in a response time of about 7.1 seconds underabout a zero applied potential. We noted the bleaching to be uniform,and the bleached appearance to be silvery.

Example 2

In this example, we chose a RMPT-HVBF₄ electrochromic pair, inconjunction with a combination of commercially available ultravioletcurable formulations, to illustrate the beneficial properties andcharacteristics of the polychromic solid film and the electrochromicinterior automotive mirrors manufactured therewith by using the sandwichlamination technique.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 2.6%; HVBF₄ (as a cathodic compound), about 1.2%; RMPT (as ananodic compound), both homogeneously dispersed in a combination of about4% propylene carbonate (as a plasticizer) and, in combination as amonomer component, about 50% “QUICK CURE” B-565 (an acrylatedurethane/ultraviolet curable formulation) and about 10% “ENVIBAR” UV1244 (a cycloalkyl epoxide/ultraviolet curable formulation). Wethoroughly mixed this electrochromic monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors by dispensinga portion of the electrochromic Monomer composition of Example 2(A),supra, onto the conductive surface of a tin oxide-coated glass substrate(the other surface of the substrate being silver-coated so as to form amirror) onto which we also placed 37 μm glass beads, and then positionedthereover the conductive surface of a clear, tin oxide-coated glasssubstrate. These glass substrates, commercially available under thetrade name “TEC-Glass” products as “TEC-20” from Libby-Owens-Ford Co.,Toledo, Ohio, having dimensions of about 3″×6″, were assembled to forman interpane distance between the glass substrates of about 37 μm. Inthis way, the electrochromic monomer composition was located between theconductive surface of the two glass substrates of the mirror assemblies.

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 9(A), supra, wasuniformly applied within the mirror assemblies of Example 9(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B. While the belt advanced initially at a rate of abouttwenty feet per minute, we exposed the assemblies to ultravioletradiation generated by the D fusion lamp of the F-300 B. We passed theassemblies under the fusion lamp light twelve times at that rate,pausing between every third or fourth pass to allow the assemblies tocool.

D. Use of Electrochromic Mirrors

We applied a potential of about 1.3 volts to one of the mirrors, andthereafter observed that the mirror colored rapidly and uniformly to abluish purple color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 57% reflectance which decreased to a lowreflectance of about 9.3%. The response time for the reflectance tochange from about 55% to about 20% was about 10 seconds when a potentialof about 1.3 volts was applied thereto. We made this determination bythe reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 50% reflectance in a response time of about 56 seconds under aboutzero applied potential. We noted the bleaching to be uniform, and thebleached appearance to be silvery.

Example 3

In this example, we compared the beneficial properties andcharacteristics of a polychromic solid film prepared using ferrocene asan anodic electrochromic compound, and manufactured within an exteriorautomotive mirror [Example 3(B)(1) and (D)(1), infra] and interiorautomotive mirrors [Example 3(B)(2) and (D)(2), infra]. We alsoinstalled an interior automotive mirror as a rearview mirror in anautomobile to observe its performance under conditions attendant withactual automotive use.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.4%-EVClO₄ (as a cathodic compound), about 2% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising, in combination as the plasticizer component, about 46.6%;propylene carbonate and about 8.8% cyanoethyl sucrose and, incombination as a monomer component, about 17.7%, caprolactone acrylateand about 13.3% polyethylene glycol diacrylate (400). We also addedabout 0.9% benzoin i-butyl ether (as a photoinitiator) and about 4.4%“UVINUL” N 35 (as an ultraviolet stabilizing agent), and thoroughlymixed this electrochromic monomer composition to ensure that ahomogeneous dispersion of the components was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

1. Exterior Automotive Mirror

We assembled exterior automotive mirrors from HW-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 3.5″×5.5″×74 g/m, with aweather barrier of an epoxy resin coupled with spacers of about 74 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 3(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

2. Interior Automotive Mirror

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×44 μm, with aweather barrier of an epoxy resin coupled with spacers of about 44 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 3(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 3(A), supra, wasuniformly applied within each of the respective mirror assemblies ofExample 3(8)(1) and (2), supra, we placed the assemblies onto theconveyor belt of a Fusion UV Curing System F-300 B, and exposed theassemblies to ultraviolet radiation in the same manner as described inExample 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors of Example 3(B), supra, and to two of the electrochromic mirrorsof Example 3(C1, supra. Our observations follow.

1. Exterior Automotive Mirror

We observed that the electrochromic mirror colored rapidly and uniformlyto a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the exterior mirror, decreased from about 80.5% to about 5.7%, with achange in the reflectance of about 70% to about 20% in a response timeof about 5.0 seconds when a potential of about 1.3 volts was appliedthereto. We made this determination by the reflectometer described inExample 1, supra.,

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 9.2 seconds, underabout a zero applied potential. We noted the bleaching to be uniform,and the bleached appearance to be silvery.

2. Interior Automotive Mirror

We observed that each of a first and second electrochromic mirrorcolored rapidly and uniformly to a blue color with a greenish hue.

In addition, we observed that for the first mirror the high reflectanceat the center portion of the interior mirror decreased from about 80.2%to about 6.3%, with a change in the reflectance of about 70% to about20% in a response time of about 3.1 seconds when a potential of about1.3 volts was applied thereto. The second mirror exhibited comparableresults, with the reflectance decreasing from about 78.4% to about 7.5%in about 2.7 seconds. We made these determinations by the reflectometerdescribed in Example 1, supra.

We also observed that the first mirror bleached from about 10%reflectance to about 60% reflectance in a response time of about 3.9seconds under about a zero applied potential, and the second mirrorbleached to the same extent in about 3.6 seconds. We noted the bleachingto be uniform, and the bleached appearance to be silvery. We havesuccessfully installed and operated such an electrochromic mirror in anautomobile as a rearview mirror and achieved excellent results.

Example 4

In this example, we chose t-butyl ferrocene as the anodic electrochromiccompound together with a monomer component containing the combination ofa monomer and a commercially available ultraviolet curable formulationto illustrate the beneficial properties, and characteristics of thepolychromic solid films made therefrom and the electrochromic interiorautomotive mirrors manufactured therewith.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.9% EVClO₄ (as a cathodic compound), about 2.3% t-butyl ferrocene(as an anodic compound), both homogeneously dispersed in a combinationcomprising about 61.7% propylene carbonate (as a plasticizer) and, incombination as a monomer component, about 10.7% caprolactone acrylateand about 10.6% “SARBOX” acrylate resin (SB 500) (an ultraviolet curableformulation). We also added about 1.3% “IRGACURE” 184 (as aphotoinitiator) and about 4.4% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-TTO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 4(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 4(A), supra, wasuniformly applied within the mirror assemblies of Example 4(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors of Example 4(B) and (C), supra, and observed this mirror tocolor rapidly and uniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 79.3% reflectance which decreased to a lowreflectance of about 9.8% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from, about 70% to about 20%when that potential was applied thereto was about 2.3 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 3.0 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Examples 5 through 8

In Examples 5 through 8, we compared the beneficial properties andcharacteristics of polychromic solid films prepared from ferrocene, andthree alkyl derivatives thereof, as the anodic electrochromic compoundand manufactured within interior automotive mirrors.

Example 5 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.5% EVClO₄ (as a cathodic compound),about 2.1% dimethyl ferrocene (as an anodic compound), bothhomogeneously dispersed in a combination of about 51.5% propylenecarbonate (as a plasticizer) and about 34.3% “QUICK CURE” B-565 (as amonomer component). We also added about 8.6% “UVINUL” N 35 (as anultraviolet stabilizing agent), and thoroughly mixed this electrochromicmonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 5(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 5(A), supra, wasuniformly applied within the mirror assemblies of Example 5(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 71.9% reflectance which decreased to a lowreflectance of about 7.5% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.4 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.2 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 6 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.5% EVClO₄ (as a cathodic compound),about 2.3% n-butyl ferrocene (as an anodic compound), both homogeneouslydispersed in a combination of about 51.3% propylene carbonate (as aplasticizer) and about 34.3% “QUICK CURE” B-565 (as a monomercomponent). We also added about 8.6% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-TTO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μm,also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 6(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 6(A), supra, wasuniformly applied within the mirror assemblies of Example 6(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 73.8% reflectance which decreased to a lowreflectance of about 7.8% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.5 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.3 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 7 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.5% EVClO₄ (as a cathodic compound),about 2.3% t-butyl ferrocene (as an anodic compound), both homogeneouslydispersed in a combination of about 51.3% propylene carbonate (as aplasticizer) and about 34.3% “QUICK CURE” B-565. (as a monomercomponent). We also added about 8.6% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion o the components wasachieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5″×10″×53 μm, with a weather barrierof an epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 7(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition as of Example 7(A), supra,was uniformly applied within the mirror assemblies of Example 7(B),supra, we placed the assemblies onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the assemblies to ultravioletradiation in the same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 73.1% reflectance which decreased to a lowreflectance of about 7.8% when about 1.3 volts was applied, thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.5 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.3 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 8 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.5% EVClO₄ (as a cathodic compound),about 1.8% ferrocene (as an anodic compound), both homogeneouslydispersed in a combination of about 51.8% propylene carbonate (as aplasticizer) and about 34.3% “QUICK CURE” B-565 (as a monomercomponent). We also added about 8.6% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5″×10″×53 μm, with a weather barrierof an epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 8(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 8(A), supra, wasuniformly applied within the mirror assemblies of Example 8(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.7% reflectance which decreased to a lowreflectance of about 7.9% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.7 seconds. We madethis determination, by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.8 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 9 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.9% EVClO₄ (as a cathodic compound), about 1.0% t-butyl ferroceneand about 1.0% DMPA (in combination as the anodic compound),homogeneously dispersed in a combination comprising about 45% propylenecarbonate, about 8.9% cyanoethyl sucrose and about 8.9%3-hydroxypropionitrile (in combination as a plasticizer component) and,in combination as a monomer component, about 17.7% caprolactoneacrylate, about 11.5% polyethylene glycol diacrylate (400) and about1.8% 1,6-hexanediol diacrylate. We also added about 0.9% “IRGACURE” 184(as a photoinitiator) and about 4.4% “UVINUL N 35” (as an ultravioletstabilizing agent), and we thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms: per square. The dimensionsof the mirror assemblies were about 2.5″×10″×44 μm, with a weatherbarrier of an epoxy resin coupled with spacers of about 44 μm alsoapplied.

We placed into these mirror assemblies the electrochromic monomercomposition, of Example 9(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 9(A), supra, wasuniformly applied within the mirror assemblies of Example 9(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed that the mirror colored rapidly anduniformly to a bluish green color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 78.2%; decreased to a low reflectance of about8.2%, with a change in the reflectance of about 70% s to about 20% in aresponse time of about 1.9 seconds when a potential of about 1.3 voltswas applied thereto. We made this determination by the reflectometerdescribed in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 5.4 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 10

In this example, like Example 2, we chose to illustrate the sandwichlamination technique of manufacturing electrochromic devices todemonstrate its efficiency in the context of the present invention.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.0% EVClO₄ (as a cathodic compound), about 1.9% t-butyl ferrocene(as an anodic compound), both homogeneously dispersed in a combinationof about 31.7% propylene carbonate (as a plasticizer), and, incombination as a monomer component, about 31.7% “QUICK CURE” B-565 andabout 31.7% Urethane Acrylate (Soft) (CN 953). We thoroughly mixed thiselectrochromic monomer composition to ensure that a homogenousdispersion of the components was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled rectangular mirrors by dispensing a portion of theelectrochromic monomer composition of Example 10(A), supra, onto theconductive surface of a silvered “TEC-20” glass substrate onto which wealso placed 150 μm glass beads, and then positioned thereover theconductive surface of a clear “TEC-20” glass substrate. We assembledthese glass substrates, having dimensions of about 5.5″×7″, undermoderate pressure to form an interpane distance between the glasssubstrates of about 150 μm. In this way, the electrochromic monomercomposition was located between the conductive surfaces of the two glasssubstrates of the mirror assemblies.

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 10(A), supra, wasuniformly applied within the mirror assemblies of Example 10(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirrors

We applied a potential of about 1.3 volts to one of the electrochromicmirror, and thereafter observed that the mirror colored rapidly anduniformly to a greenish blue color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 66.7% reflectance which decreased to a lowreflectance of about 5.8%. The response time for the reflectance tochange from about 60% to about 5.9% was about 30 seconds when apotential of about 1.3 volts was applied thereto. We made thisdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 5.9% reflectance toabout 60% reflectance in a response time of about 180 seconds underabout zero applied potential.

Example 11

In this example, we chose to illustrate the beneficial properties andcharacteristics of the polychromic solid films manufactured withinelectrochromic glazings, that may be used as small area transmissivedevices, such as optical filters and the like.

A. Preparation of Electrochromic Monomer Composition

We prepared am electrochromic monomer composition comprising by weightabout 2.5% HVBF₄ (as a cathodic compound), about 1.1%—MPT—having beenpreviously reduced by contacting with zinc [see Varaprasad IV andcommonly assigned U.S. patent application Ser. No. 07/935,784, now U.S.Pat. No. 5,500,760] (as an anodic compound), both homogeneouslydispersed in a combination comprising, in combination as a plasticizer,about 47.7% propylene carbonate and about 1% acetic acid, and about47.7% “QUICK CURE” B-565 (as a monomer component). We thoroughly mixedthis electrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Glazing Assembly With Electrochromic Monomer Composition

We assembled electrochromic glazings from HW-ITO coated glass substrates(where the conductive surface of each glass substrate faced oneanother), with the glass having a sheet resistance of about 15 ohms persquare. The dimensions of the glazing assemblies were about 2.5″×10″×53μm, with a weather barrier of an epoxy resin coupled with spacers ofabout 53 μm also applied.

We placed into these glazing assemblies the electrochromic monomercomposition of Example 11 (A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Glazingto Polychromic Solid Film

Once the electrochromic composition of Example 11(A), supra, wasuniformly applied within the glazing assemblies of Example 11(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1 (D), supra.

D. Use of Electrochromic Glazing

We applied a potential of about 1.3 volts to the electrochromic glazingsof Example 11(B) and (C), supra. We observed that the electrochromicglazings colored rapidly and uniformly to a bluish purple color.

In addition, we observed that the high transmission at the centerportion of the glazing decreased from about 79.2% to about 7.4%, with achanged transmission of about 70% to about 20% in a response time ofabout 4.4 seconds when a potential of about 1.3 volts was appliedthereto. We made this determination by the detection method described inExample 1, supra, except that the reflectometer was set in transmissionmode.

We also observed that the glazing bleached from about 15% transmissionto about 60% transmission in a response time of about 8.4 seconds, underabout a zero applied potential. We noted good cycle stability,ultraviolet stability and thermal stability.

Example 12 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.7% HVBF₄ (as a cathodic compound), about 1.6% RMPT (as an anodiccompound), both homogeneously dispersed in a combination comprisingabout 46.2% 3-hydroxypropionitrile (as a plasticizer), and, incombination as a monomer component, about 23.1%2-(2-ethoxyethoxy)-ethylacrylate and about 23.1% tetraethylene glycoldiacrylate. We also added about 2.3% “ESACURE” TZT (as aphotoinitiator), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled electrochromic mirrors from “TEC-20” glass substrates(where the conductive surface of each glass substrate faced oneanother), having dimensions of about 2.5″×10″×37 μm, with a weatherbarrier of an epoxy resin coupled with spacers of about 37 μm alsoapplied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 12(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 12(A), supra, wasuniformly applied within the mirror assemblies of Example 12(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors of Example 12(B) and (C), supra, and observed this mirror tocolor rapidly and uniformly to a bluish purple color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 68.4% reflectance which decreased to a lowreflectance of about 13.3% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 65% to about 20%when that potential was applied thereto was about 3.0 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 15% reflectance toabout 60% reflectance in a response time of about 3.0 seconds underabout a zero applied potential. We noted the bleaching to be uniform,and the bleached appearance to be silvery,

Example 13

In this example, we chose to illustrate the beneficial properties andcharacteristics of polychromic solid films manufactured withinelectrochromic glazings consisting of sun roofs using a compatibilizingplasticizer component. Also, in this example, we chose to formulate theelectrochromic monomer composition with an additional monomer havingpolyfunctionality as a compatibilizing agent for the polychromic solidfilm.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 4.0% HVBF₄ (as a cathodic compound),about 1.7% RMPT (as an anodic compound), both homogeneously dispersed ina combination comprising, in combination as a plasticizer, about 10.2%propylene carbonate, about 17% benzyl acetone and about 14.7% cyanoethylsucrose, and, in combination as a monomer component, about 33.5% “QUICKCURE” B-565 and about 18.9% polyethylene glycol diacrylate (400). Wethoroughly mixed this electrochromic monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Glazing Assembly with Electrochromic Monomer Composition

We constructed a glazing assembly consisting of a sun roof model bydispensing a portion of the electrochromic monomer composition ofExample 13 (A), supra, onto the conductive surface of a “TEC-10” glasssubstrate onto which we also placed 100 μm glass beads, and thenpositioned thereover another “TEC-10” glass substrate, so that theelectrochromic monomer composition was between and in contact with theconductive surface of the two glass substrates. We used “TEC-10” glasssubstrates having dimensions of about 6″×16.5°, with bus bars attachedat the lengthwise side of the substrates to create a distancetherebetween of about 16.5″. The interpane distance between the “TEC-10”glass substrates was about 100 μm.

C. Transformation of Electrochromic Monomer Composition Within GlazingAssembly to Polychromic Solid Film

Once the electrochromic monomer composition of Example 13 (A), supra,was uniformly applied within the glazing assembly of Example 13(B),supra, we placed the assembly onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the assembly to ultraviolet radiationin the same manner as described in Example 2(C), supra.

D. Use of Electrochromic Glazing Assembly

We applied a potential of about 1.3 volts to the glazing assembly, andthereafter observed the assembly to color rapidly and uniformly to abluish purple color.

In addition, we observed that the high transmission at the centerportion of the glazing assembly was about 60.7% transmission whichdecreased to a low transmission of about 6.0% when about 1.3 volts wasapplied thereto. The response time for the transmission to change fromabout 60% to about 10% when that potential was applied thereto was about3.8 minutes. We made this determination by the detection methoddescribed in Example 1, supra, except that the reflectometer was set intransmission mode.

We also observed that the glazing assembly bleached from about 10%transmission to about 45% transmission in a response time of about 4.2minutes under about a zero applied potential.

Example 14

In this example, we chose to manufacture large area electrochromicmirrors, by the two hole filling technique, to demonstrate thebeneficial properties and characteristics of the polychromic solid filmswithin large truck mirrors.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 1.9% EVClO₄ (as a cathodic compound), about 1.2% RMPT (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 53.3% propylene carbonate (as a plasticizer) and about43.6% “QUICK CURE” B-565 (as a monomer component). We thoroughly mixedthis electrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled large truck mirrors from FW-ITO glass substrates (where theconductive surface of each glass substrate faced one another), with theclear, front glass and the silvered, rear glass having a sheetresistance of about 6 to about 8 ohms per square. The dimensions of themirror assemblies were about 6.5″×15′×44 μm, with a weather barrier ofan epoxy resin coupled with spacers of about 44 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 14(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 14(A), supra, wasuniformly applied within the truck mirror assemblies of Example 14(B),supra, we placed the assemblies onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the assemblies to ultravioletradiation in the same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromictruck mirrors, and thereafter observed that the mirror colored rapidlyand uniformly to a bluish purple color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 67.4% decreased to a low reflectance of about7.9%, with a changed reflectance of about 65% to about 20% in a responsetime of about 7.1 seconds when a potential of about 1.3 volts wasapplied thereto. We made this determination by the reflectometerdescribed in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 55% reflectance in a response time of about 15.0 seconds underabout a zero applied potential, and to its high reflectance shortlythereafter.

The electrochromic truck mirrors performed satisfactorily with its longaxis positioned in vertical alignment with the ground.

Example 15

In this example, we have illustrated that the electrochromic monomercomposition may be prepared in stages and thereafter used to manufacturepolychromic solid films, and electrochromic devices manufactured withsame, that demonstrates the beneficial properties and characteristicsherein described. Also, in this example, like Examples 12 and 13, supra,we chose to formulate the electrochromic monomer composition with adifunctional monomer component to illustrate the properties andcharacteristics attendant with the addition of that component.

A. Preparation of Electrochromic Monomer Composition

The electrochromic monomer composition of this example comprised byweight about 3.9% EVClO₄ (as a cathodic compound), about 2.3% t-butylferrocene (as an anodic compound), both homogeneously dispersed in acombination of about 62% propylene carbonate (as the plasticizer), and,in combination as a monomer component, about 20% caprolactone acrylateand about 6.5% polyethylene glycol diacrylate (400). We also added about0.9% “IRGACURE” 184 (as a photoinitiator) and about 4.4% “UVINUL” N 35(as an ultraviolet stabilizing agent), and thoroughly mixed thiselectrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

We prepared the above composition by first combining the propylenecarbonate, caprolactone acrylate, polyethylene glycol diacrylate (400)and “IRGACURE” 184, with stirring and bubbling nitrogen gas through thecombination, and initiating cure by exposing this combination to asource of fluorescent light at room temperature for a period of time ofabout 10 minutes.

At this point, we removed the source of fluorescent light, and combinedtherewith the EVClO₄, t-butyl ferrocene and “UVINUL” N 35 to obtain ahomogeneously dispersed electrochromic monomer composition. We monitoredthe extent of cure by the increase of viscosity.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled interior automotive mirrors with HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5″×10″×53 μm, with a weather barrierof an epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 15(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 15(A), supra, wasuniformly applied within the mirror assemblies of Example 15(B), supra.,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Mirrors

We applied a potential of about 1.3 volts to one of the mirrors, andthereafter observed that the mirror colored rapidly and uniformly to ablue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 82.6% reflectance which decreased to a lowreflectance of about 8.8%. The response time for the reflectance tochange from about 70% to about 20% was about 2.5 seconds at about roomtemperature and about the same when the surrounding temperature wasreduced to about −28° C. when a potential of about 1.3 volts was appliedthereto. We made that determination by the reflectometer described inExample 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 1.9 seconds at aboutroom temperature and of about 7.4 seconds when the surroundingtemperature was reduced to about −28° C. under about zero appliedpotential.

Example 16

In this example, we chose to manufacture the polychromic solid film froma commercially available epoxy resin together with a cross-liking agentto illustrate enhanced prolonged coloration performance attained whensuch combinations are used in the electrochromic monomer composition.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.7% HVBF₄ (as a cathodic compound), about 1.7% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 64.5% propylene carbonate (as a plasticizer) and about26.5% “CYRACURE” resin UVR-6105 (as a monomer component) and about 1.2%2-ethyl-2-(hydroxymethyl)-1,3-propanediol (as a cross-linking agent). Wealso added about 1.4% “CYRACURE” UVI-6990 (as a photoinitiator), andthoroughly mixed this electrochromic monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled interior automotive mirrors HWG-ITO coated glass substrates(where the conductive surface of each glass substrate faced oneanother), with the clear, front glass and silvered, rear glass having asheet resistance of about 15 ohms per square. The dimensions of themirror assemblies were about 2.5″×10″×53 μm, with a weather barrier ofan epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 16(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 16(A), supra, wasuniformly applied within the mirror assemblies of Example 16(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors prepared according to Examples 16(B) and (C), supra, andobserved this mirror to color rapidly and uniformly to a blue color witha greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 80.0% reflectance which decreased to a lowreflectance of about 7.3% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.9 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 3.8 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

We further observed that the mirror bleached uniformly andsatisfactorily after prolonged coloration in excess of about 8 hours.

Example 17

In this example, like Example 16, we chose to manufacture polychromicsolid films from a commercially available epoxy resin together with across-linking agent to illustrate enhanced prolonged colorationperformance attained when such combinations are used in theelectrochromic monomer composition.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 4.7% HVBF₄ (as a cathodic compound),about 1.4% ferrocene (as an anodic compound), both homogeneouslydispersed in a combination of about 64.6% propylene carbonate (as aplasticizer), about 17.5% “CYRACURE” resin UVR-6105 (as a monomercomponent) and about 10.1% “CARBOWAX” PEG 1450 (as a cross-linkingagent). We also added about 1.4% “CYRACURE” UVI-6990 (as aphotoinitiator), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5″×10″×53 μm, with a weather barrierof an epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 17(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 17(A), supra, wasuniformly applied within the mirror assemblies of Example 17(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 75.2% reflectance which decreased to a lowreflectance of about 7.6% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.4 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.2 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

We further observed that the mirror bleached uniformly andsatisfactorily after prolonged coloration in excess of about 8 hours.

Example 18

In this example, we chose ferrocene as the anodic electrochromiccompound together with a monomer component containing the combination ofa monofunctional monomer and a difunctional monomer to illustrate thebeneficial properties and characteristics of polychromic solid filmsmade therefrom.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.3% EVClO₄ (as a cathodic compound), about 1.9% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 55.9% propylene carbonate (as a plasticizer) and, incombination as a monomer component, about 12.7% caprolactone acrylateand about 17.2% polyethylene glycol diacrylate (400). We also addedabout 3.5% benzoin i-butyl ether (as a photoinitiator) and about 4.3%“UVINUL” N 35 (as an ultraviolet stabilizing agent), and thoroughlymixed this electrochromic monomer composition to ensure that ahomogenous dispersion of the components was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×44 μm, with aweather barrier of an epoxy resin coupled with spacers of about 44 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 18(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 18(A), supra, wasuniformly applied within the mirror assemblies of Example 18(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B. While the belt advanced initially at a rate of aboutfifty feet per minute, we exposed the assemblies to ultravioletradiation generated by the D fusion lamp of the F-300 B. We passed thesemirror assemblies under the fusion lamp fifteen times pausing for twominute intervals between every third pass, then nine times at that ratepausing for two minute intervals between every third pass, and finallysix times at a rate of about twenty-five feet per minute pausing for twominute intervals after every other pass.

D. Use of Electrochromic Mirror

We applied a potential of about 1.5 volts to one of the electrochromicmirrors of Examples 18(B) and (C), supra, and observed this mirror tocolor rapidly and uniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 77.1% reflectance which decreased to a lowreflectance of about 7.9% when about 1.5 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.8 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 2.6 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 19

In this example, we chose ferrocene as the anodic electrochromiccompound together with a monomer component containing the combination ofa monomer and a commercially available ultraviolet curable formulationto illustrate the beneficial proper ties and characteristics ofpolychromic solid films made therefrom.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.3% EVClO₄ (as a cathodic compound), about 1.9% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about55.9% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 10.3% caprolactone acrylate, about 15.5%polyethylene glycol diacrylate (400) and about 4.3% “SARBOX” acrylateresin (SB 500). We also added about 3.5% benzoin i-butyl ether (as aphotoinitiator) and about 4.3% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled interior automotive mirrors with HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 19(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 19(A), supra, wasuniformly applied within the mirror assemblies of Example 19(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 18(C), supra.

D. Use of Electrochromic Mirrors

We applied a potential of about 1.5 volts to one of the mirrors, andthereafter observed that the mirror colored rapidly and uniformly to ablue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 79.6% reflectance which decreased to a lowreflectance of about 7.6%. The response time for the reflectance tochange from about 70% to about 20% was about 2.2 seconds when apotential of about 1.5 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 2.5 seconds underabout zero applied potential.

Example 20

In this example, we chose to manufacture interior rearview mirrors frompolychromic solid films prepared with a commercially available epoxyresin together with a cross-linking agent to illustrate enhancedprolonged coloration performance attained when such combinations areused in the electrochromic monomer composition.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.61% EVClO₄ (as a cathodic compound), about 2.1% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 57.4% propylene carbonate (as a plasticizer) and, inCombination as a monomer component, about 8.2% “CYRACURE” resin UVR-6105and about 14.0% caprolactone, and about 1.1%2-ethyl-2-(hydroxymethyl)-1,3-propanediol (as a cross-linking agent). Wealso added, in combination as photoinitiators, about 1.4% “CYRACURE”UVI-6990 and about 1.5% benzoin i-butyl ether, and thoroughly mixed thiselectrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled interior automotive mirrors HWG-ITO coated glass substrates(where the conductive surface of each glass substrate faced oneanother), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5″×10″×44 μm, with a weather barrierof an epoxy resin coupled with spacers of about 44 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 20(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 20(A), supra, wasuniformly applied within the mirror assemblies of Example 20(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors prepared according to Examples 20(B) and (C), supra, andobserved this mirror to color rapidly and uniformly to a blue color witha greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 76.9% reflectance which decreased to a lowreflectance of about 7.9% when about 1.4 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 3.1 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 3.3 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 21

In this example, we illustrate that a prolonged application of a bleachpotential—i.e., a potential having a polarity opposite to that used toachieve color—having a magnitude greater than about 0.2 volts, andpreferably about 0.4 volts, may be used to enhance bleach speeds ofelectrochromic devices, such as automotive rearview mirrors,manufactured with polychromic solid films as the medium of variablereflectance.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.3% EVClO₄ (as a cathodic compound), about 1.9% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 60.2% propylene carbonate (as a plasticizer) and, incombination as a monomer component, about 8.6% caprolactone acrylate,about 12.9% polyethylene glycol diacrylate (400) and about 4.3% “SARBOX”acrylate resin (SB 500). We also added about 3.4% “IRGACURE” 184 (as aphotoinitiator) and about 4.3% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled interior automotive mirrors from HW-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the front, clear glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×44 μm, with aweather barrier of an epoxy resin coupled with spacers of about 44 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 21(A), supra, using the vacuum backfillingtechnique (as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 21(A), supra, wasuniformly applied within the mirror assemblies of Example 21(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about −0.7 volts to one of the electrochromicmirrors of Examples 21(B) and (C), supra, and observed that mirrorreflectance at the center portion of the mirror remained high at about76%.

Upon reversing the polarity of the applied potential and increasing themagnitude to about +1.5 volts, we observed this mirror to color rapidlyand uniformly to a blue color.

In addition, we observed that the high reflectance at the center portionof the mirror decreased to a low reflectance of about 7.8%, with theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto being about 2.4 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 1.7 seconds under apotential of about −0.7 volts with a high reflectance of about 78%reestablished. We noted that when a potential of about zero volts toabout −0.2 volts was applied to the mirror to bleach the mirror from thefully dimmed stated, the response time to achieve this effect was about2.0 seconds. We also noted that when a potential having a greatermagnitude, such as about −0.8 volts to about −0.9 volts, was applied tothe mirror, the color assumed by the polychromic solid film may becontrolled. For instance, a slight blue tint may be achieved at thataforestated greater negative potential using the electrochromic systemof this example so that the bleached state of the electrochromic mirrormay be matched to the color appearance of conventional nonelectrochromicblue-tint mirrors commonly featured on luxury automobiles.

Example 22

In this example, we illustrate that a gradient opacity panel, such asthat which may be used as an electrochromic shade band on an automobilewindshield, may be created by configuring the bus bars on theelectrochromic assembly so they are affixed partially around, or alongthe opposite sides, of the assembly, thus creating a transition betweenthe areas of the device to which voltage is applied and those where novoltage is applied.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 2.1% EVClO₄ (as a cathodic compound), about 1.4% t-butyl ferrocene(as an anodic compound), both homogeneously dispersed in a combinationof about 54.2% propylene carbonate (as the plasticizer), and, incombination as a monomer component, about 28.6% B-565 and about 13.8%Urethane Acrylate (Soft) (CM 953). We thoroughly mixed thiselectrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Panel Assembly With Electrochromic Monomer Composition

We constructed a panel assembly containing an electrochromic shade bandby dispensing a portion of the electrochromic monomer composition ofExample 22(A), supra, onto the conductive surface of a HW-ITO coatedglass substrate having a sheet resistance of about 15 ohms per square.Onto this substrate we also placed 100 μm glass beads, and thenpositioned thereover another HW-ITO coated glass substrate having asheet resistance of about 15 ohms per square so that the electrochromicmonomer composition was between and in contact with the conductivesurface of the two glass substrates. The dimensions of the assembly wereabout 4.5″×14″, with an interpane distance between the glass substratesof about 100 μm.

We connected bus bars along the 14″ sides of the panel assembly onlyabout 4″ inward from the edge of each of the opposing 14″ sides. Wethereafter affixed electrical leads to the bus bars.

C. Transformation of Electrochromic Monomer Composition Within PanelAssembly to Polychromic Solid Film

Once the electrochromic monomer composition of Example 22(A), supra, wasuniformly applied within the window panel assembly of Example 22(B),supra, we placed the assembly onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the panel assembly to ultravioletradiation in the same manner as described in Example 2(C), supra.

Once the polychromic solid film was formed, we applied a weather barrierof epoxy resin along, and over, the glass joints to prevent entry ofenvironmental contaminants. This weather barrier consisted of a bead of“ENVIBAR” UV 1244 ultraviolet curable adhesive followed by theapplication of “SMOOTH-ON” room temperature cure epoxy (commerciallyavailable from Smooth-On Inc., Gillette, N.J.).

D. Demonstration of Electrochromic Shade Band Within Panel Assembly

We applied a potential of about 1.3 volts to the panel assembly, andthereafter observed that only the 4″ region through which an electricfield was formed colored rapidly, uniformly and intensely to a bluecolor. We also observed that color extended beyond that 4″ region for adistance of about 1″ in a gradient opacity which changed gradually froman intense coloration immediately adjacent the bus bar/non-bus bartransition to a bleached appearance beyond that additional 1″ region orthereabouts.

In addition, we observed that the high transmittance at the centerportion of the panel assembly was about 79.6% transmittance whichdecreased to a low transmittance of about 7.6%. The response time forthe transmittance to change from about 70% to about 20% was about 2.2seconds when a potential of about 1.5 volts was applied thereto. We madethat determination by the reflectometer described in Example 1, supra,except that the reflectometer was set in transmission mode.

We also observed that the panel assembly bleached from about 10%transmittance to about 60% transmittance in a response time of about 2.5seconds under about zero applied potential.

Example 23

In this example, like Example 3, supra, we installed the interiorautomotive mirror as a rearview mirror in an automobile to observe itsperformance under conditions attendant with actual use.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.0% EVClO₄ (as a cathodic compound), about 1.3% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about62.6% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 8.9% caprolactone acrylate, about 13.4%polyethylene glycol diacrylate (400) and about 4.5% “SARBOX” acrylateresin (SB 500). We also added about 1.8% “IRGACURE” 184 (as aphotoinitiator) and about 4.5% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogenous dispersion of the components wasachieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled an interior automotive mirror with HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×74 μm, with aweather barrier of an epoxy resin coupled with spacers of about 74 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 23(A), supra, using the vacuum backfillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 23(A), supra, wasuniformly applied within the mirror assembly of Example 23(B), supra, weplaced the assembly onto the conveyor belt of a Fusion UV Curing SystemF-300 B, and exposed the assembly to ultraviolet radiation in the samemanner as described in Example 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.5 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.0%; reflectance which decreased to a lowreflectance of about 7.5%. The response time for the reflectance tochange from about 70% to about 20% was about 3.5 seconds when apotential of about 1.5 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 5.2 seconds underabout zero applied potential.

We have successfully installed and operated this mirror in an automobileas a rearview mirror and have achieved excellent results.

Example 24

In this example, we chose to illustrate the beneficial properties andcharacteristics of polychromic solid films manufactured within anelectrochromic sun roof panel.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 1.4 EVClO₄ (as a cathodic compound),about 0.9% t-butyl ferrocene (as an anodic compound), both homogeneouslydispersed in a combination comprising about 39% propylene carbonate (asa plasticizer), and, in combination as a monomer component, about 39%“QUICK CURE” B-565 and about 19.53% Urethane Acrylate (Soft) (CM 953).We thoroughly mixed this electrochromic monomer composition to ensurethat a homogeneous dispersion of the components was achieved.

B. Preparation of Sun Roof Panel Assembly and Placement ofElectrochromic Monomer Composition Therein

We prepared the glass substrates for use in the glazing assembly of thisexample by placing flat “TEC-20” glass substrates (with a black ceramicfrit band around their perimeter edge regions), having dimensions ofabout 12″×16″, onto the mold of a bending instrument at room temperatureunder ambient conditions, and then increasing the temperature of thesubstrates to be bent to at least about 500° C. thereby causing thesubstrates to conform to the shape of the mold.

We also placed, as a spacer means, black drafting tape (Zipatone, Inc.,Hillsdale, Ill.), having a width of about 0.0625″ and a thickness ofabout 150 μm, onto a conductive surface of one of the bent “TEC-20”glass substrates in about 1.5″ intervals across the width of thesubstrate. At such intervals, we found the black drafting tape to bepositioned in an aesthetically appealing manner, and to maintainuniformity of the electrochromic media across the full dimensions of thepanel.

We assembled the sun roof panel by dispensing a portion of theelectrochromic monomer composition of Example 24(A), supra, onto theconductive surface of the substrate to be used as the concave interiorsurface (i.e., the Number 4 surface), and placed thereover theconductive surface of the substrate bearing the spacer means so that theelectrochromic monomer composition was between and in contact with theconductive surface of the glass substrates. We then placed the panelassembly in a vacuum bag, gently elevated the temperature and evacuatedsubstantially most of the air from the vacuum bag. In this way, theelectrochromic monomer composition dispersed uniformly between thesubstrates under the pressure from the atmosphere.

C. Transformation of Electrochromic Monomer Composition Into PolychromicSolid Film

We then placed the sun roof panel assembly (still contained in thevacuum bag) into a Sunlighter model 1530 UV chamber, equipped with threemercury lamps (commercially available from Test-Lab Apparatus Co.,Milford, N.H.), and allowed the sun roof panel to remain exposed to theultraviolet radiation emitted by the lamps for a period of time of about30 minutes. The interpane distance between the “TEC-20” glass substrateswas about 150 μm.

We thereafter attached bus bars at the 12″ side of the substrates tocreate a distance therebetween of about 16″. We then attached electricalleads to the bus bars.

D. Use of Electrochromic Sun Roof Panel

We applied a potential of about 1.3 volts to the glazing assembly, andthereafter observed the panel to color rapidly and uniformly to a bluishpurple color.

In addition, we observed that the high transmission at the centerportion of the sun roof panel was about 67% transmission which decreasedto a low transmission of about 5% when about 1.3 volts was appliedthereto. The response time for the transmission to change from about 60%to about 10% when that potential was applied thereto was about 3minutes. We made this determination by the detection method described inExample 1, supra, except that the reflectometer was set in transmissionmode.

We also observed that the glazing assembly bleached from about 5%transmission to about 60% transmission in a response time of about 6.5minutes under about a zero applied potential.

The ultraviolet stability, scatter safety performance and/orelectrochromic performance, and reduction in transmittance ofnear-infrared radiation of sun roof panels manufactured in accordancewith the teaching herein, may be augmented by using the methods taughtin Lynam III and Lynam V, and in commonly assigned U.S. Pat. No.5,239,406 (Lynam).

Example 25

In this example, we chose to illustrate the beneficial properties andcharacteristics of polychromic solid films manufactured within anelectrochromic sun visor having a segmented design.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 2.4% EVClO₄ (as a cathodic compound),about 1.6% ferrocene (as an anodic compound), both homogeneouslydispersed in a combination comprising about 48% propylene carbonate (asa plasticizer), and, in combination as a monomer component, about 32%“QUICK CURE” B-565 and about 16% Urethane Acrylate (Soft) (CN 953). Wethoroughly mixed this electrochromic monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Sun Visor with Electrochromic Monomer Composition

We assembled the sun visor of this example from FW-ITO coated glasssubstrates, having dimensions of about 4″×14″ and a sheet resistance ofabout 6 to about 8 ohms per square, onto which we previously placeddeletion lines to form three individual segments. We created thesedeletion lines by screening a photo-resist material onto the glasssubstrate prior to depositing the ITO coating, and thereafter applying acoat of ITO onto the photo-resist coated substrate, and washing away thephotoetched resist material using an organic solvent, such as acetone.

We assembled the sun visor by placing onto the 14″ edges of theconductive surface of one of the FW-ITO glass substrates “KAPTON” hightemperature polyamide tape (E.I. du Pont de Nemours and Company,Wilmington, Del.), having a thickness of 70 μm. We then dispensed aportion of the electrochromic monomer composition of Example 25(A),supra, onto that conductive surface and then placed thereover theconductive surface of another substrate so that the electrochromicmonomer composition was between and in contact with the conductivesurface of the glass substrates. The interpane distance between thesubstrates was about 70 μm.

C. Transformation of Electrochromic Monomer Composition Within Sun Visorto Polychromic Solid Film

Once the electrochromic monomer composition of Example 25(A), supra, wasuniformly applied within the sun visor assembly of Example 25(B), supra,we placed the assembly onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assembly to ultraviolet radiation in thesame manner as described in Example 2(C), supra,

Upon completion of the transformation process, we applied “ENVIBAR” UV1244 to the glass edges and joints and again exposed the sun visor toultraviolet radiation to further weather barrier protect the sun visor.We then applied “SMOOTH-ON” epoxy to those portions of the sun visor toform a final weather barrier about the sun visor.

D. Use of Electrochromic Sun Visor

We applied a potential of about 1.3 volts to the sun visor, andthereafter observed the sun visor to color rapidly and uniformly to abluish purple color.

In addition, we observed that the high transmission at the centerportion of the sun visor was about 74.9% transmission which decreased toa low transmission of about 2.5% when about 1.5 volts was appliedthereto. The response time for the transmission to change from the hightransmission state to about 10% when that potential was applied theretowas about 9 seconds. We made this determination by the detection methoddescribed in Example 1, supra, except that the reflectometer was set intransmission mode.

We also observed that the sun visor bleached from about 10% transmissionto about 70% transmission in a response time of about 15 seconds underabout a zero applied potential.

The segmented portions of the sun visor of this example may be made in ahorizontal direction or a vertical direction, and individual segmentsmay be activated by connection to an individual segment addressingmeans, such as a mechanical switch, a photosensor, a touch sensor,including a touch activated glass panel, a voice activated sensor, an RFactivated sensor and the like. In addition, segments may be activatedindividually or as pluralities by responding to glare from the sun, suchas when the sun rises from and falls toward the horizon, or as ittraverses the horizon. This sun visor, as well as other electrochromicglazings, such as windows, sun roofs and the like, may use automaticglare sensing means that involve single or multiple photosensors, suchas those disclosed in U.S. Pat. No. 5,148,014 (Lynam).

Example 26

In this example, we assembled an interior automotive mirror as arearview mirror, to be installed in an automobile to observe itsperformance under conditions attendant with actual use.

A. Preparation of Electrochromic 1 Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.6% EVClO₄ (as a cathodic compound), about 1.6% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about61.9% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 11.1% polyethylene glycol monomethacrylate(400), about. 11.1% polyethylene glycol diacrylate (400) and about 4.4%“SARBOX” acrylate resin (SB 500). We also added about 1.8% “IRGACURE”184 (as a photoinitiator) and about 4.4% “UVINUL” N 35 (as anultraviolet stabilizing agent), and thoroughly mixed this electrochromicmonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled an interior automotive mirror with HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 26(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 26(A), supra, wasuniformly applied within the mirror assembly of Example 26(B), supra, weplaced the assembly onto the conveyor belt of a Fusion UV Curing SystemF-300 B, and exposed the assembly to ultraviolet radiation in the samemanner as described in Example 1 (D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.5 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.0% reflectance which decreased to a lowreflectance of about 7.4%. The response time for the reflectance tochange from about 70% to about 20% was about 2.1 seconds when apotential of about 1.5 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.0 seconds underabout zero applied potential.

Example 27

In this example, we assembled automotive mirrors for use with the 1993Lincoln Continental automobile. Specifically, Example 27(A), infra,illustrates the manufacture and use of an interior rearview mirror, andExample 27(B), infra, illustrates the use of an exterior mirror, sizedfor driver-side and passenger-side applications, to be installed in theautomobile.

A. 1993 Lincoln Continental Interior Rearview Mirror

1. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.6% EVClO₄ (as a cathodic compound), about 1.6% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about62% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 8.9% caprolactone acrylate, about 13.3%polyethylene glycol diacrylate (400) and about 4.4% “SARBOX” acrylateresin (SB 500). We also added about 1.8% “IRGACURE” 184 (as aphotoinitiator) and about 4.4% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

2. Interior Rearview Mirror Assembly With Electrochromic MonomerComposition

We assembled an interior rearview mirror, with an interpane distance of53 μm, from HWG-ITO coated 093 glass substrates (where the conductivesurface of each glass substrate faced one another), with both the clear,front glass and the silvered, rear glass having a sheet resistance ofabout 15 ohms per square. We also applied a weather barrier of an epoxyresin coupled with spacers of about 53 μm,

We placed into these mirror assemblies the electrochromic monomercomposition of Example 27(A)(1), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

3. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 27(A)(1), supra,was uniformly applied within the mirror assembly of Example 27(A)(2),supra, we placed the assembly onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the assembly to ultraviolet radiationin the same manner as described in Example 1 (D), supra.

4. Use of Electrochromic Mirror

We applied a potential of about 1.5 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 76.5% reflectance which decreased to a lowreflectance of about 7.4%. The response time for the reflectance tochange from about 70% to about 20% was about 2.2 seconds when apotential of about 1.5 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 2.7 seconds underabout zero applied potential.

B. 1993 Lincoln Continental Exterior Mirrors—Driver-Side andPassenger-Side

1. Preparation of Electrochromic Monomer Composition.

We prepared an electrochromic monomer composition comprising by weightabout 2.6% EVClO₄ (as a cathodic compound), about 1.2% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about63% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 9% caprolactone acrylate, about 13.5%polyethylene glycol diacrylate (400) and about 4.5% “SARBOX” acrylateresin (SB 500). We also added about 1.8% “IRGACURE” 184 (as aphotoinitiator) and about 4.5% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

2. Exterior Mirror Assemblies With Electrochromic Monomer Composition

We assembled exterior mirrors, with an interpane distance of 74 μm, fromFW-ITO coated 063 glass substrates (where the conductive surface of eachglass substrate faced one another), with both the clear, front glass andthe silvered, rear glass having a sheet resistance of about 6 to about 8ohms per square. We also applied a weather barrier of an epoxy resincoupled with spacers of about 74 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 27(B)(1), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

3. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 27(B)(1), supra,was uniformly applied within the mirror assemblies of Example 27(B)(2),supra, we placed the assemblies onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the assemblies to ultravioletradiation in the same manner as described in Example 1(D), supra.

4. Use of Electrochromic Mirrors

We applied a potential of about 1.5 volts to one of the mirrors, andthereafter observed rapid and uniform coloration to a blue color with agreenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72% reflectance which decreased to a lowreflectance of about 8%. The response time for the reflectance to changefrom about 70% to about 20% was about 3.9 seconds when a potential ofabout 1.5 volts was applied thereto. We made that determination by thereflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.0 seconds underabout zero applied potential.

Example 28 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 6.31% HVSS (as a cathodic compound), about 1.63% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about47.48% propylene carbonate and about 8.63% 3-hydroxypropionitrile (as aplasticizer), and, in combination as a monomer component, about 12.95%caprolactone acrylate, about 8.63% polyethylene glycol diacrylate (400)and about 8.63% “SARBOX” acrylate resin (SB 501). We also added, incombination as photoinitiators, about 0.13% “IRGACURE” 184 and about1.29%, “CYRACURE” UVI-6990 and about 4.32% “UVINUL” N 35 (as anultraviolet stabilizing agent), and thoroughly mixed this electrochromicmonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled an interior rearview mirror, with an interpane distance of53 μm, from HWG-ITO coated 093 glass substrates (where the conductivesurface of each glass substrate faced one another), with both the clear,front glass and the silvered, rear glass having a sheet resistance ofabout 15 ohms per square. We also applied a weather barrier of an epoxyresin coupled with spacers of about 53 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 28(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 28(A), supra, wasuniformly applied within the mirror assembly of Example 28(B), supra, weplaced the “SARBOX” acrylate resin (SB 500E50) and about 4.37%“CYRACURE” resin UVR-6110. We also added, in combination asphotoinitiators, about 0.44%; “IRGACURE” 184 and about 1.31% “CYRACURE”UVI-6990 and about 4.37% “UVINUL” N 35 (as an ultraviolet stabilizingagent), and thoroughly mixed this electrochromic monomer composition toensure that a homogeneous dispersion of the components was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled an interior rearview mirror, with an interpane distance of53 μm, from HWG-ITO coated 093 glass substrates (where the conductivesurface of each glass substrate faced one another), with both the clear,front glass and the silvered, rear glass having a sheet resistance ofabout 15 ohms per square. We also applied a weather barrier of an epoxyresin coupled with spacers of about 53 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 28(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 28(A), supra, wasuniformly applied within the mirror assembly of Example 28(B), supra, weplaced the assembly onto the conveyor belt of a Hanovia UV Curing System(Hanovia Corp., Newark, N.J.), fitted with UV lamp 6506A431, with theintensity dial set at 300 watts. We exposed the assembly to ultravioletradiation in a similar manner as described in Example 1 (D), supra, bypassing the assembly under the UV lamp with the conveyor speed set atabout 20% to about 50% for about 120 to about 180 multiple passes.

D. Use of Electrochromic Mirror

We applied a potential of about 1.2 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 73.9% reflectance which decreased to a lowreflectance of about 7.4%. The response time for the reflectance tochange from about 70% to about 20% was about 3.9 seconds when apotential of about 1.2 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

Example 29 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.38% DSMVClO₄ (as a cathodic compound) and about 0.57% EHPVClO₄(as a cathodic compound), about 1.62% ferrocene (as an anodic compound),both homogeneously dispersed in a combination of about 56.74% propylenecarbonate (as a plasticizer), and, in combination as a monomercomponent, about 13.10% caprolactone acrylate, about 8.73% polyethyleneglycol diacrylate (400), about 4.37% “SARBOX” acrylate resin (SB 500E50)and about 4.37% “CYRACURE” resin UVR-6110. We also added, in combinationas photoinitiators, about 0.44% “IRGACURE” 184 and about 1.31%“CYRACURE” UVI-6990 and about 4.37% “UVINUL” N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled an interior rearview mirror, with an interpane distance of53 μm, from HWG-ITO coated 093 glass substrates (where the conductivesurface of each glass substrate faced one another), with both the clear,front glass and the silvered, rear glass having a sheet resistance ofabout 15 ohms per square. We also applied a weather barrier of an epoxyresin coupled with spacers of about 53 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 29(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition. Within Mirrorto Polychromic Solid Film

Once the electrochromic monomer composition of Example 29(A), supra, wasuniformly applied within the mirror assembly of Example 29(B), supra, weplaced the assembly onto the conveyor belt of a Hanovia UV Curing System(Hanovia Corp., Newark, N.J., fitted with UV lamp 6506A431, with theintensity dial set at 300 watts. We exposed the assembly to ultravioletradiation in a similar manner as described in Example 1(D), supra, bypassing the assembly under the UV lamp with the conveyor speed set atabout 20% to about 50% for about 120 to about 180 multiple passes.

D. Use of Electrochromic Mirror

We applied a potential of about 1.2 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 79.6% reflectance which decreased to a lowreflectance of about 6.7%. The response time for the reflectance tochange from about 70% to about 20% was about 2.8 seconds when apotential of about 1.2 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

Example 30 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.42% DSMVClO₄ (as a cathodic compound) and about 0.59% EHPVClO₄(as a cathodic compound), about 1.65% ferrocene (as an anodic compound),both homogeneously dispersed in a combination of about 48.67% propylenecarbonate (as a plasticizer), and, in combination as a monomercomponent, about 13.27% caprolactone acrylate, about 8.85% polyethyleneglycol diacrylate (400), about 8.85% “SARBOX” acrylate resin (SB 500E50)and about 8.85% “CYRACURE” resin UVR-6110. We also added, in combinationas photoinitiators, about 0.44% “IRGACURE” 184 and about 1.77%“CYRACURE” UVI-6990 and about 2.65% 2-hydroxy-4-octoxybenzophenone (asan ultraviolet stabilizing agent), and thoroughly mixed thiselectrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Mirror Assembly With Electrochromic Monomer Composition

We assembled an interior rearview mirror, with an interpane distance of53 μm, from HWG-ITO coated 093 glass substrates (where the conductivesurface of each glass substrate faced one another), with both the clear,front glass and the silvered, rear glass having a sheet resistance ofabout 15 ohms per square. We also applied a weather barrier of an epoxyresin coupled with spacers of about 53 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 30(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition Within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 30(A), supra, wasuniformly applied within the mirror assembly of Example 30(B), supra, weplaced the assembly onto the conveyor belt of a Hanovia UV Curing System(Hanovia Corp., Newark, N.J., fitted with UV lamp 6506A431, with theintensity dial set at 300 watts. We exposed the assembly to ultravioletradiation in a similar manner as described in Example 1 (D), supra, bypassing the assembly under the UV lamp with the conveyor speed set atabout 20% to about 50% for about 120 to about 180 multiple passes.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 71% reflectance which decreased to a lowreflectance of about 6.9%. The response time for the reflectance tochange from about 70% to about 20% was about 3.9 seconds when apotential of about 1.3 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

Example 31 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.36% HUVPF₆ (as a cathodic compound), about 0.97% EVCl0₄ (as acathodic compound), about 0.17% Ferrocene (FE, an anodic compound),about 0.39% 5,10-dihydro-5,10-dimethylphenazine (as an anodic compound),all homogeneously dispersed in a combination of about 89.68% propylenecarbonate (as plasticizer) and, in combination as a monomer component,about 0.65% HDT (an isocyanate) and about 3.08% Lexorez 1931-50 (apolyol), and about 0.03% T−1 (a tin catalyst), and about 4.67% Uvinul N35 (a UV stabilizer). We thoroughly mixed this monomer composition toensure that a homogeneous dispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×125 μm, with aweather barrier of an epoxy resin coupled with spacers of about 125 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 31 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 31 (A), supra,was uniformly applied within the mirror assemblies of Example 31 (B),supra, we placed the assemblies overnight at room temperature duringwhich time the monomer composition reacted to form in situ the solidpolymer matrix film inside the mirror. These mirror assemblies were thenplaced in an electrically heated convection oven maintained at about 80°C. for about 2 hours.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with bluish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.3% reflectance which decreased to a lowreflectance of about 7.1% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.1 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 7.0 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 32 A. Preparation of Prepolymer Composition that Includes aViologen Containing Polyol

We prepared viologen containing polyol through copolymerization ofESMVClO₄ with caprolactone acrylate according to the followingprocedure: We prepared a reaction mixture comprising by weight about4.86% ESMVCLO₄ (a viologen with vinyl functionality), about 1.94% UVI6990 (a photoinitiator), about 0.97% Irgacure 184 (a photoinitiator),all homogeneously dispersed in a combination comprising about 43.69%caprolactone acrylate (an acrylate with hydroxyl functionality) and48.54% propylene carbonate and placed it in a sealed glass container. Weplaced the sealed glass container on a conveyor belt of a Fusion UVCuring System F-300B. While the belt advanced at a rate of about 10 feetper minute, we exposed the reaction mixture to ultraviolet radiationgenerated by the D fusion lamp of the F 300B. We passed the sealed glasscontainer containing the reaction mixture under the fusion lamp lighttwenty five times at that rate, pausing momentarily between the passesto allow the prepolymer composition to cool. We used the resultingprepolymer composition that includes a viologen containing polyol toprepare the electrochromic monomer composition.

B. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 2.11^(%) prepolymer composition of Example 32 (A), supra (as acathodic compound and polyol), about 1.97% EVCl0₄ (as a cathodiccompound), and about 1.01% 5,10-dihydro-5,10-dimethylphenazine (as ananodic compound), all homogeneously dispersed in a combination of about76.65% propylene carbonate (as plasticizer) and in combination as amonomer component, about 2.68% HDT (an isocyanate) and about 15.52%Desmophen 1700 (a polyol), and about 0.06% T-9 (a tin catalyst). Wethoroughly mixed this monomer composition to ensure that a homogeneousdispersion of the components was achieved.

C. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 32 (B), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

D. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 32 (B), supra,was uniformly applied within the mirror assemblies of Example 32 (C),supra, we placed the assemblies overnight at room temperature duringwhich time the monomer composition reacted to form in situ the solidpolymer matrix film inside the mirror. These mirror assemblies were thenplaced in an electrically heated convection oven maintained at about 80°C. for about 2 hours.

E. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 64.1% reflectance which decreased to a lowreflectance of about 6.5% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 60% to about 20%when that potential was applied thereto was about 2.6 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 50% reflectance in a response time of about 12.7 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 33 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.3% HHVPF₆ (as a cathodic compound), about 0.97% EVCl0₄ (as acathodic compound), about 0.59% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), all homogeneously dispersed in a combination ofabout 89.71% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 0.65% HDT (an isocyanate) and about 3.08%Lexorez 1931-50 (a polyol), and about 0.03% T-9 (a tin catalyst), andabout 4.67% Uvinul N 35 (a UV stabilizer). We thoroughly mixed thismonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC 15and from HW-ITO glass substrates (where the conductive surface of eachglass substrate faced one another), with both the clear, front glass andthe silvered, rear glass having a sheet resistance of about 15 ohms persquare. The dimensions of the mirror assemblies were about 2.5″×10″×105μm, with a weather barrier of an epoxy resin coupled with spacers ofabout 105 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 33 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 33 (A), supra,was uniformly applied within the mirror assemblies of Example 33 (B),supra, we placed the assemblies in an electrically heated convectionoven maintained at about 80° C. for about 2 hours whereupon the monomercomposition reacted to form in situ the solid polymer matrix film insidethe mirror.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 71.8% reflectance which decreased to a lowreflectance of about 7,0% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.2 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.9 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

E. Stability and Cyclability of Electrochromic Devices Manufactured withPolychromic Solid Films

To demonstrate the cycle stability of the electrochromic mirrorsassemblies of Example 33 (B and C), supra, we subjected theelectrochromic mirrors made from TEC 15 glass substrates to 20 secondscolor—20 seconds bleach cycles at different test temperatures requiredby automotive specifications. We have observed good cycle stabilityafter about 85,000 cycles which include about 25,000 cycles at 70° C.,about 20,000 cycles at −30° C., and about 40,000 cycles at roomtemperature. We observed, that the high reflectance of the mirror at thecenter portion of the mirror changed from 71.8% to 71.0% and that thelow reflectance changed from 7.0% to 7.5% after about 85,000 cycles. Wealso observed that the response time for reflectance change from about70% to about 20% changed from 2.2 seconds to 2.7 seconds and theresponse time for reflectance change from about 10% to about 60% changedfrom 4.9 seconds to 5.2 seconds after about 85,000 cycles.

To demonstrate the ultraviolet stability, we exposed the electrochromicmirror assemblies made from HW-ITO glass substrate of Example 33 supra,to at least about 2600 kJ/m² using a Xenon weatherometer as per SAEJ1960. We observed, that the high reflectance of the mirror at thecenter portion of the mirror changed from 79.4% to 78.9% and that thelow reflectance changed from 6.0% to 6.25% after exposure to ultravioletradiation. We also observed that the response time for reflectancechange from about 70% to about 20% changed from 1.6 seconds to 1.7seconds and the response time for reflectance change from about 10% toabout 60% changed from 4.1 seconds to 4.4 seconds after exposure toultraviolet radiation.

To demonstrate the thermal stability of the electrochromic mirrorassemblies of Example 33 (B and C), supra, we placed the mirrorassemblies made from HW-ITO glass substrates in an electric ovenmaintained at about 85° C. for at least about 400 hours. We observed,that the high reflectance of the mirror at the center portion of themirror changed from 79% to 77% and that the low reflectance changed from6.1% to 5.7% after the heat test. We also observed that the responsetime for reflectance change from about 70% to about 20% changed from 1.5seconds to 1.7 seconds and the response time for reflectance change fromabout 10% to about 60% changed from 4.1 seconds to 4.4 seconds after theheat test.

The environmental and overall performance the electrochromic mirrors wassuitable for use in a vehicle.

Example 34 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.37% HUVPF₆ (as a cathodic compound), about 0.96% EVClO₄ (as acathodic compound), about 0.59% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), all homogeneously dispersed in a combination ofabout 89.65% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 0.65% HDT (an isocyanate) and about 3.08%Lexorez 1931-50 (a polyol), and about 0.03% T−1 (a tin catalyst), andabout 4.67% Uvinul N 35 (a UV stabilizer). We thoroughly mixed thismonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror assembly with Electrochromic Monomer Composition

In this example, we assembled exterior automotive mirrors using TEC 15glass for the front substrate and a multi-layer metal reflector coatedglass (consisting of about 200 angstroms of rhodium undercoated withabout 1500 angstroms of chromium, and with the chromium being disposedbetween the rhodium layer and the glass surface so as to serve as anadhesion promoter layer such as is described in U.S. application Ser.No. 08/238,521 filed May 5, 1994, now U.S. Pat. No. 5,668,663, thedisclosure of which is hereby incorporated by reference herein) for therear substrate (where the conductive surface of each glass substratefaced one another), with the clear front glass having a sheet resistanceof about 15 ohms per square and the rear multi-layered reflector coatedglass having a sheet resistance of about 5 ohms per square. Thedimensions of the mirror assemblies were about 3.5″×7.5″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 34 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 34 (A), supra,was uniformly applied within the mirror assemblies of Example 34 (B),supra, we placed the assemblies in an electrically heated convectionoven maintained at about 80° C. for about 2 hours whereupon the monomercomposition reacted to form in situ the solid polymer matrix film insidethe mirror.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 56.3% reflectance which decreased to a lowreflectance of about 7.0% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 55% to about 20%when that potential was applied thereto was 1.2 seconds. We made thisdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 50% reflectance in a response time of about 5.8 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 35 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 1.09% HUVPF₆ (as a cathodic compound), about 0.58% EVCl0₄ (as acathodic compound), about 0.59% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), all homogeneously dispersed in a combination ofabout 89.34% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 0.84% HDT (an isocyanate) and about 2.88%Lexorez 1931-50 (a polyol), and about 0.03% T−1 (a tin catalyst), andabout 4.65% Uvinul N 35 (a UV stabilizer). We thoroughly mixed thismonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier, of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 35 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 35 (A), supra,was uniformly applied within the mirror assemblies of Example 35 (B),supra, we placed the assemblies overnight at room temperature duringwhich time the monomer composition reacted to form in situ the solidpolymer matrix film inside the mirror. These mirror assemblies were thenplaced in an electrically heated convection oven maintained at about 80°C. for about 2 hours.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.1% reflectance which decreased to a lowreflectance of about 7.3% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.0 seconds. We madethis determination by the reflectonmeter described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 7.9 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 36 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.3% HHVPF₆ (as a cathodic compound), about 0.96% EVCl0₄ (as acathodic compound), about 0.59% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), all homogeneously dispersed in a combination ofabout 84.13% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 1.38% HDT (an isocyanate) and about 7.96%Lexorez 1931-50 (a polyol), and about 0.01% T-9 (a tin catalyst), andabout 4.67% Uvinul N 35 (a UV stabilizer). We thoroughly mixed thismonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 36 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 36 (A), supra,was uniformly applied within the mirror assemblies of Example 36 (B),supra, we placed the assemblies in an electrically heated convectionoven maintained at about 80° C. for about 2 hours whereupon the monomercomposition reacted to form in situ the solid polymer matrix film insidethe mirror.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 69.9%; reflectance which decreased to a lowreflectance of about 8.0% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.1 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 5.2 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 37 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.65% HUVClO₄ (as a cathodic compound), about 0.77% EVCl0₄ (as acathodic compound), about 0.59% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), all homogeneously dispersed in a combination ofabout 89.57% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 0.79% HDT (all isocyanate) and about 2.94%Lexorez 1931-50 (a polyol), and about 0.03% T−1 (a tin catalyst), andabout 4.66% Uvinul N 35 (a UV stabilizer). We thoroughly mixed thismonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 37 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 37 (A), supra,was uniformly applied within the mirror assemblies of Example 37 (B),supra, we placed the assemblies overnight at room temperature duringwhich time the monomer composition reacted to form in situ the solidpolymer matrix film inside the mirror. These mirror assemblies were thenplaced in an electrically heated convection oven maintained at about 80°C. for about 2 hours.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 74.0% reflectance which decreased to a lowreflectance of about 7.5% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.0 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 6.2 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 38 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.52% HUEVCl0₄ (as a cathodic compound), about 0.77% EVCl0₄ (as acathodic compound), about 0.59% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), all homogeneously dispersed in a combination ofabout 88.75% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 0.93% HDT (an isocyanate) and about 3.74%Lexorez 1931-50 (a polyol), and about 0.03% T−1 (a tin catalyst), andabout 4.67% Uvinul N 35 (a UV stabilizer). We thoroughly mixed thismonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 38 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 38 (A), supra,was uniformly applied within the mirror assemblies of Example 38 (B),supra, we placed the assemblies overnight at room temperature duringwhich time the monomer composition reacted to form in situ the solidpolymer matrix film inside the mirror. These mirror assemblies were thenplaced in an electrically heated convection oven maintained at about 80°C. for about 2 hours.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.9% reflectance which decreased to a lowreflectance of about 7.1% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.0 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 5.4 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 39 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.3% HHVPF₆ (as a cathodic compound), about 0.96% EVCl0₄ (as acathodic compound), about 0.49% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), and about 0.13% THAc having been previously reducedby contacting with zinc (U.S. Pat. No. 5,500,760 issued Mar. 19, 1996the disclosure of which is incorporated by reference herein) (as ananodic compound), all homogeneously dispersed in a combination of about85.34% propylene carbonate and about 0.91% acetic acid (as plasticizer)and, in combination as a monomer component, about 1.59% HDT (anisocyanate) and about 5.42% Lexorez 1931-50 (a polyol), and about 0.19%T-9 (a tin catalyst), and about 4.67% Uvinul N 35 (a UV stabilizer). Wethoroughly mixed this monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×110″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 39 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 39 (A), supra,was uniformly applied within the mirror assemblies of Example 39 (B),supra, we placed the assemblies in an electrically heated convectionoven maintained at about 80° C. for about 2 hours whereupon the monomercomposition reacted to form in situ, the solid polymer matrix filminside the mirror.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 67.4% reflectance which decreased to a lowreflectance of about 6.6% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 65% to about 20%when that potential was applied thereto was about 2.5 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 8.3 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 40 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.3% HHVPF₆ (as a cathodic compound), about 0.97% EVCl0₄ (as acathodic compound), about 0.59% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), all homogeneously dispersed in a combination ofabout 89.71% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 0.65% HDT (an isocyanate) and about 3.08%Lexorez 1931-50 (a polyol), and about 0.03% T-9 (a tin catalyst), andabout 4.67% Uvinul N 35 (a UV stabilizer). We thoroughly mixed thismonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled exterior automotive mirrors using clearHW-ITO glass for the front substrate and chromium metal coated glass forthe rear substrate (where the conductive surface of each glass substratefaced one another), with the clear front glass having a sheet resistanceof about 15 ohms per square and the rear chrome glass having a sheetresistance of 5 ohms per square. The dimensions of the mirror assemblieswere about 3.5″×7.5″×105 μm, with a weather barrier of an epoxy resincoupled with spacers of about 105 μm also applied.

We placed into these exterior mirror assemblies the electrochromicmonomer composition of Example 40 (A), supra, using the vacuum backfilling technique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychramic Solid Film

Once the electrochromic monomer composition of Example 40 (A), supra,was uniformly applied within the mirror assemblies of Example 40 (B),supra, we placed the assemblies in an electrically heated convectionoven maintained at about 80° C. for about 2 hours whereupon the monomercomposition reacted to form in situ the solid polymer matrix film insidethe mirror.

D. Use of Exterior Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 52.7% reflectance which decreased to a lowreflectance of about 6.4%; when about 1.4 volts was applied to thereto.The response time for reflectance to change from high reflectance toabout 23% when that potential was applied thereto was about 1.6 seconds.We made this determination by the reflectometer described in Example 1,supra.

We also observed that the mirror bleached from low reflectance to about40%, reflectance in a response time of about 6.9 seconds under about azero applied potential. We noted the bleaching to be uniform.

E. Stability and Cyclability of Electrochromic Devices Manufactured withPolychromic Solid Films

To demonstrate the electrical stability of the mirror assemblies ofExample 40 (B and C), supra, we applied 1.4 volts and continuouslycolored the electrochromic mirrors for at least about 300 hours at roomtemperature. We observed that the high reflectance changed from 52.7% to52.2% and the low reflectance remained unchanged at 6.4% after thecontinuous coloration test. We observed that the response time forreflectance to change from high reflectance to about 23% changed from1.6 seconds to 2.0 seconds after the continuous coloration test and alsothat the response time for the mirror to bleach from low reflectance toabout 40% reflectance remained steady at about 6.9 seconds before andafter the continuous coloration test.

To demonstrate the cyclability of the mirror assemblies of Example 40 (Band C), supra, we applied 1.4 volts and continuously colored theelectrochromic mirrors for at least about 300 hours at room temperature.

To demonstrate the cycle stability of the electrochromic mirrorsassemblies of Example 40 (B and C), supra, we subjected theelectrochromic mirrors to 20 seconds color—20 seconds bleach cycles atdifferent test temperatures required by automotive specifications. Weobserved good cycle stability after about 80,000 cycles which includeabout 30,000 cycles at 70° C., and about 50,000 cycles at roomtemperature. We observed, that the high reflectance of the mirror at thecenter portion of the mirror changed from 53.22 to 51.1% and that thelow reflectance changed from 6.5% to 7.1% after the cycle test. We alsoobserved that the response time for reflectance change from highreflectance to about 23% remained constant at about 1.9 seconds afterthe cycle test and the response time for reflectance change from lowreflectance to about 40% changed from 5.7 seconds to 5.5 seconds afterthe cycle test.

Example 41

In this example, we chose to illustrate the beneficial properties andcharacteristics of the polychromic solid films manufactured withinelectrochromic glazings, or that may be used as small area transmissivedevices, such as optical filters and the like.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.37% HUVPF₆ (as a cathodic compound), about 0.96% EVCl0₄ (as acathodic compound), about 0.59% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), all homogeneously dispersed, in a combination ofabout 89.65% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 0.65% HDT (an isocyanate) and about 3.08%Lexorez 1931-50 (a polyol), and about 0.03% T−1 (a, tin catalyst), andabout 4.67% Uvinul N 35 (a UV stabilizer). We thoroughly mixed thismonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Glazing Assembly with Electrochromic Monomer Composition

In this example, we assembled electrochromic glazings from clear TEC 15glass substrates (where the conductive surface of each glass substratefaced one another), with the glass having a sheet resistance of about 15ohms per square. The dimensions of the glazing assemblies were about2.5″×10″×105 μm, with a weather barrier of an epoxy resin coupled withspacers of about 105 μm also applied.

We placed into these glazing assemblies the electrochromic monomercomposition of Example 41 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Glazingto Polychromic Solid Film

Once the electrochromic monomer composition of Example 41 (A), supra,was uniformly applied within the glazing assemblies of Example 41 (B),supra, we placed the assemblies in an electrically heated convectionoven maintained at about 80° C. for about 2 hours whereupon the monomercomposition reacted to form in situ the solid polymer matrix film insidethe glazing assemblies.

D. Use of Electrochromic Glazing

We applied a potential of about 1.4 volts to one of the electrochromicglazings of Example 41 (B and C), supra. We observed that theelectrochromic glazings colored rapidly and uniformly to a gray colorwith greenish hue.

In addition, we observed that the high transmission at the centerportion of the glazing was about 77.1% transmission which decreased to alow transmission of about 10.3% when about 1.4 volts was applied tothereto. The response time for transmission to change from about 70% toabout 20% when that potential was applied thereto was 4 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the glazing bleached from about 10% transmissionto about 70% transmission in a response time of about 7.7 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 42 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.3% DVAVPF₆ (as a cathodic compound), about 1.15% EVCl0₄ (as acathodic compound), about 0.69% 5,10-dihydro-5,10-dimethylphenazine (asan anodic compound), all homogeneously dispersed in a combination ofabout 86.63% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 0.93% HDT (an isocyanate) and about 5.59%Lexorez 1931-50 (a polyol), and about 0.05% dibutyltin dilaurate (a tincatalyst), and about 4.66% Uvinul N 35 (a UV stabilizer). We thoroughlymixed this monomer composition to ensure that a homogeneous dispersionof the components was achieved.

B. Mirror assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 42 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 42 (A), supra,was uniformly applied within the mirror assemblies of Example 42 (B),supra, we placed the assemblies in an electrically heated convectionoven maintained at about 60° C. for about 1 hour whereupon the monomercomposition reacted to form in situ the solid polymer matrix film insidethe mirror.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 68.0% reflectance which decreased to a lowreflectance of about 6.7%, when about 1.2 volts was applied to thereto.The response time for reflectance to change from about 60% to about 20%when that potential was applied thereto was about 2.4 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10, reflectance toabout 60% reflectance in a response time of about 5.7 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 43 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 2.18% HUVPF₆ (as a cathodic compound), about 0.58%5,10-dihydro-5,10-dimethylphenazine (as an anodic compound), allhomogeneously dispersed in a combination of about 88.87% propylenecarbonate (as plasticizer) and, in combination as a monomer component,about 1.3% HDT (an isocyanate) and about 2.41% Lexorez 1931-50 (apolyol), and about 0.03% T−1 (a tin catalyst), and about 4.63% Uvinul N35 (a UV stabilizer). We thoroughly mixed this monomer composition toensure that a homogeneous dispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 43 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 43 (A), supra,was uniformly applied within the mirror assemblies of Example 43 (B),supra, we placed the assemblies in an electrically heated convectionoven maintained at about 80° C. for about 1 hour whereupon the monomercomposition reacted to form in situ, the solid polymer matrix filminside the mirror.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 71.2% reflectance which decreased to a lowreflectance of about 12.5% when about 1.2 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 5.3 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 15% reflectance toabout 50% reflectance in a response time of about 12.0 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 44 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.66% HVSS (as a cathodic compound), about 1.52% EVCl0₄ (as acathodic compound), about 0.17% ferrocene (as an anodic compound), about0.74% phenothiazine (as an anodic compound) all homogeneously dispersedin a combination of about 87.6% propylene carbonate (as plasticizer)and, in combination as a monomer component, about 4.61%dipentaerythritol pentaacrylate. We also added about 0.09%1,1′-azobiscyclohexanecarbonitrile (as an initiator), about 4.61% UvinulN 35 (a UV stabilizer). We thoroughly mixed this monomer composition toensure that a homogeneous dispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from HW-ITOglass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×125 μm, with aweather barrier of an epoxy resin coupled with spacers of about 125 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 44 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 44 (A), supra,was uniformly applied within the mirror assemblies of Example 44 (B),supra, we placed the assemblies in an electrically heated convectionoven maintained at about 80° C. for about 2 hour whereupon the monomercomposition reacted to form in situ the solid polymer matrix film insidethe mirror.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with bluish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 65% reflectance which decreased to a lowreflectance of about 6% when about 1.3 volts was applied to thereto. Wemade this determination by the reflectometer described in Example 1,supra. We noted that the response time to color and also the responsetime to bleach the mirror was suitable for use in a vehicle.

Example 45 Synthesis of Ferrocene-Polyol

We prepared ferrocene-polyol through copolymerization of vinyl ferrocene(VFE), hydroxyethyl acrylate (HEA) and methyl methacrylate (MMA)according to the following procedure: We prepared a reaction mixturecomprising about 1 gm VFE, about 0.25 gm HEA, about 10.0 gm MMA andabout 0.33 gm 1.1′-azobiscyclohexanecarbonitrile (an initiator), allhomogeneously dispersed in toluene and placed it in a glass container.We thoroughly purged the reaction mixture with oxygen-free nitrogen gas.We then sealed the glass container and heated the reaction mixture in anoven maintained at about 80° C. for about 75 hours. We then allowed thereaction mixture to cool to room temperature and poured it into a largequantity of heptane to isolate the ferrocene-polyol. We then purifiedthe yellow solid by reprecipitation from heptane. We used the resultingferrocene-polyol prepolymer that includes ferrocene (an anodic compound)and reactive hydroxyl functionalities to prepare electrochromic monomercompositions. Thus one embodiment of this invention uses electrochromicmonomer compositions comprising at least one ferrocene-polyol (as ananodic compound) and at least one cathodic electrochromic compound. Thecomposition may also include other anodic compounds and plasticizers asdesired.

We also prepared other ferrocene-polyols by using different weightratios of monomers, VFE:HEA:MMA, using the same procedure. In additionother ferrocene-polyols are prepared from monomer mixtures such ascaprolactone acrylate & methyl methacrylate and hydroxyethylmethacrylate & methyl methacrylate, each in combination with vinylferrocene as a comonomer by using similar procedures.

Example 46 Synthesis of Polymethyl Methacrylate-Polyol

We prepared polymethyl methcrylate containing reactive hydroxylfunctionalities through copolymerization of hydroxyethyl acrylate (HEA)and methyl methacrylate (MMA.) according to the following procedure: Weprepared a reaction mixture comprising about 0.25 gm HEA, about 10.0 gmMMA and about 0.3 μm 1.1′-azobiscyclohexanecarbonitrile (an initiator),all homogeneously dispersed in toluene and placed it in a glasscontainer. We thoroughly purged the reaction mixture with oxygen-freenitrogen gas. We then sealed the glass container and heated the reactionmixture in an oven maintained at about 80° C. for about 75 hours. Wethen allowed the reaction mixture to cool to room temperature and pouredit into a large quantity of heptane to isolate the polymethylmethacrylate-polyol. We then purified the white solid by reprecipitationfrom heptane. We used the resulting polymethyl methacrylate-polyolprepolymer that contains reactive hydroxyl functionalities to preparethe electrochromic monomer compositions.

We also prepared other polymethyl methacrylate-polyols by usingdifferent weight ratios of monomers, HEA:MMA, using the same procedure.

Example 47 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.80% HUVCl0₄ (as a cathodic compound), about 0.87% EVClO₄ (as acathodic compound), about 1.10% Ferrocene-Polyol (as an anodiccompound), about 0.09% Ferrocene (as an anodic compound), about 0.49%5,10-dihydro-5,10-dimethylphenazine (as an anodic compound), allhomogeneously dispersed in a combination of about 88.5% propylenecarbonate (as plasticizer) and, in combination as a monomer component,about 0.89% HDT (an isocyanate) and about 2.60% Lexorez 1931-50 (apolyol), and about 0.014% T−1 (a tin catalyst), and about 4,60% Uvinul N35 (a UV stabilizer). We thoroughly mixed this monomer composition toensure that a homogeneous dispersion of the components was achieved.

B. Mirror assembly with Electrochromic Monomer Composition

In this example, we assembled exterior automotive mirrors using HW-ITOglass for the front substrate and a multi-layer Metal reflector coatedglass (consisting of about 200 angstroms of rhodium undercoated withabout 1500 angstroms of chromium, and with the chromium being disposedbetween the rhodium layer and the glass surface so as to serve as anadhesion promoter layer such as is described in U.S. Pat. No. 5,668,663and U.S. Pat. No. 5,724,187, the disclosures of which are herebyincorporated by reference herein) for the rear substrate (where theconductive surface of each glass substrate faced one another), with theclear front glass having a sheet resistance of about 15 ohms per squareand the rear multi-layered reflector coated glass having a sheetresistance of about 5 ohms per square. The dimensions of the mirrorassemblies were about 5.0″×8.0″×125 μm, with a weather barrier of anepoxy resin coupled with an anhydride curing agent and spacers of about125 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 47(A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 47(A), supra, wasuniformly applied within the mirror assemblies of Example 47(B), supra,we placed the assemblies in an electrically heated convection ovenmaintained at about 80° C. for about 2 hours whereupon the monomercomposition reacted to form in situ the solid polymer mat ix film insidethe mirror.

Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agreen color with bluish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 64.5% reflectance which decreased to a lowreflectance of about 5.4% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 60% to about 20%when that potential was applied thereto was 3.2 seconds. We made thisdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 50% reflectance in a response time of about 10.4 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 48 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.80% HUVClO₄ (as a cathodic compound), about 0.87% EVClO₄ (as acathodic compound), about 1.10% Ferrocene-Polyol (as an anodiccompound), about 0.09% Ferrocene (as an anodic compound), about 0.49%5,10-dihydro-5,10-dimethylphenazine (as an anodic compound), allhomogeneously dispersed in a combination of about 57.6%tertraethyleneglycol dimethylether and about 31.0% tetramethylenesulfone(as plasticizer) and, in combination as a monomer component, about 0.89%HDT (an isocyanate) and about 2.60% Lexorez 1931-50 (a polyol), andabout 0.03% T−1 (a tin catalyst), and about 4.60% Uvinul N 35 (a UVstabilizer). We thoroughly mixed this monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×88 μm, with aweather barrier of an epoxy resin coupled with an imidazole curing agentand spacers of about 88 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 48(A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 48(A), supra, wasuniformly applied within the mirror assemblies of Example 48(B), supra,we placed the assemblies overnight at room temperature during which timethe monomer composition reacted to form in situ the solid polymer matrixfilm inside the mirror. These mirror assemblies were then placed in anelectrically heated convection oven maintained at about 80° C. for about2 hours.

Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 74.1% reflectance which decreased to a lowreflectance of about 8.3% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.0 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 11.4 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 49 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.80% HUVCl0₄ (as a cathodic compound), about 0.87%-EVCl0₄ (as acathodic compound), about 1.10% Ferrocene-Polyol (as an anodiccompound), about 0.09% Ferrocene (as an anodic compound), about 0.49%5,10-dihydro-5,10-dimethylphenazine (as an anodic compound), allhomogeneously dispersed in a combination of about 83.9% propylenecarbonate (as plasticizer) and, in combination as a monomer component,about 1.44% HDT (an isocyanate) and about 5.84% Lexorez 1931-50 (apolyol), and about 0.03% T−1 (a tin catalyst), 0.82% polymethylmethacrylate-polyol and about 4.60% Uvinul N 35 (a UV stabilizer). Wethoroughly mixed this monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Mirror assembly with Electrochromic Monomer Composition

In this example, we assembled exterior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 3.5″×5″×125 μm, with aweather barrier of an epoxy resin coupled with spacers of about 125 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 49(A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 49(A), supra, wasuniformly applied within the mirror assemblies of Example 49(B), supra,we placed the assemblies overnight at room temperature during which timethe monomer composition reacted to form in situ the solid polymer matrixfilm inside the mirror. These mirror assemblies were then placed in anelectrically heated convection oven maintained at about 80° C. for about2 hours.

Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.3% reflectance which decreased to a lowreflectance of about 6.8% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 4.5 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 11.8 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 50 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 1.0% HUVCl0₄ (as a cathodic compound), about 0.57% EVCl0₄ (as acathodic compound), about 0.78% Ferrocene-Polyol (as an anodiccompound), about 0.03% Ferrocene (as an anodic compound), about 0.39%5,10-dihydro-5,10-dimethylphenazine (as an anodic compound), allhomogeneously dispersed in a combination of about 89.4% propylenecarbonate (as plasticizer) and, in combination as a monomer component,about 1.06% HDT (an isocyanate) and about 2.2% Lexorez 1931-50 (apolyol), and about 0.03% T−1 (a tin catalyst), and about 4.60 Uvinul N35 (a UV stabilizer). We thoroughly mixed this monomer composition toensure that a homogeneous dispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 50(A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 50(A), supra, wasuniformly applied within the mirror assemblies of Example 50(B), supra,we placed the assemblies overnight at room temperature during which timethe monomer composition reacted to form in situ the solid polymer matrixfilm inside the mirror. These mirror assemblies were then placed in anelectrically heated convection oven maintained at about 80° C. for about2 hours.

Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with bluish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 73.9% reflectance which decreased to a lowreflectance of about 7.1%-when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 1.7 seconds, We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 9.0 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 51 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.64% HUVCl0₄ (as a cathodic compound), about 0.76% EVCl0₄ (as acathodic compound), about 1.56% Ferrocene-Polyol (as an anodiccompound), about 0.03% Ferrocene (as an anodic compound), about 0.39%5,10-dihydro-5,10-dimethylphenazine (as an anodic compound), allhomogeneously dispersed in a combination of about 88.9% propylenecarbonate (as plasticizer) and, in combination as a monomer component,about 1.05% HDT (an isocyanate) and about 2.2% Lexorez 1931-50 (apolyol), and about 0.03% T−1 (a tin catalyst), and about 4.60% Uvinul N35 (a UV stabilizer). We thoroughly mixed this monomer composition toensure that a homogeneous dispersion of the components was achieved.

B. Mirror assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10′×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 51 (A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 51(A), supra, wasuniformly applied within the mirror assemblies of Example 51 (B), supra,we placed the assemblies overnight at room temperature during which timethe monomer composition reacted to form in situ the solid polymer matrixfilm inside the mirror. These mirror assemblies were then placed in anelectrically heated convection oven maintained at about 80° C. for about2 hours.

Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 73.6% reflectance which decreased to a lowreflectance of about 7.5% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 1.8 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 6.7 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 52 At Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.60% HUPPVCl0₄ (as a cathodic compound), about 1.11% PPVCl0₄ (asa cathodic compound), about 0.59% DMPA (as an anodic compound), allhomogeneously dispersed in a combination of about 88.75% propylenecarbonate (as plasticizer) and, in combination as a monomer component,about 0.93% HDT (an isocyanate) and about 3.74% Lexorez 1931-50 (apolyol), and about 0.03% T−1 (a tin catalyst), and about 4.67% Uvinul N35 (a UV stabilizer). We thoroughly mixed this monomer composition toensure that a homogeneous dispersion of the components was achieved.

B. Mirror assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 52(A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 52(A), supra, wasuniformly applied within the mirror assemblies of Example 52(B), supra,we placed the assemblies overnight at room temperature during which timethe monomer composition reacted to form in situ the solid polymer matrixfilm inside the mirror. These mirror assemblies were then placed in anelectrically heated convection oven maintained at about 80° C. for about2 hours.

Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 71.8% reflectance which decreased to a lowreflectance of about 7.4% when about 1.4 volts was applied to thereto.The response time for reflectance to change from about 70% to about 20%when that potential was applied thereto was about 1.9 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 6.2 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 53

In this example, we chose to illustrate the beneficial properties andcharacteristics of the polychromic solid films manufactured withinelectrochromic glazings, or that may be used as small area transmissivedevices, such as optical filters and the like.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 1.12% HUVPF₆ (as a cathodic compound), about 0.67% EVCl0₄ (as acathodic compound), about 3.85% Ferrocene-polyol (as an anodiccompound), about 0.30% Ferrocene (as an anodic compound), allhomogeneously dispersed in a combination of about 85.32% propylenecarbonate (as plasticizer) and, in combination as a monomer component,about 1.01% HDT (an isocyanate) and about 2.39% Lexorez 1931-50 (apolyol), and about 0.85% polymethyl methacrylate and about 0.013% T−1 (atin catalyst), and about 4.48% Uvinul N 35 (a UV stabilizer). Wethoroughly mixed this monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Glazing Assembly with Electrochromic Monomer Composition

In this example, we assembled electrochromic glazings from clear TEC 15glass substrates (where the conductive surface of each glass substratefaced one another), with the glass having a sheet resistance of about 15ohms per square. The dimensions of the glazing assemblies were about2.5″×10″×105 μm, with a weather barrier of an epoxy resin coupled withspacers of about 105 μm also applied.

We placed into these glazing assemblies the electrochromic monomercomposition of Example 53(A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Glazingto Polychromic Solid Film

Once the electrochromic monomer composition of Example 53(A), supra, wasuniformly applied within the glazing assemblies of Example 53(B), supra,we placed the assemblies in an electrically heated convection ovenmaintained at about 80° C. for about 2 hours whereupon the monomercomposition reacted to form in situ the solid polymer matrix film insidethe glazing assemblies.

Use of Electrochromic Glazing

We applied a potential of about 1.4 volts to one of the electrochromicglazings of Example 53(B and C), supra. We observed that theelectrochromic glazings colored rapidly and uniformly to a gray colorwith greenish hue.

In addition, we observed that the high transmission at the centerportion of the glazing was about 71.3% transmission which decreased to alow transmission of about 13.2% when about 1.4 volts was applied tothereto. We made this determination by the reflectometer described inExample 1, supra. We noted the bleaching to be uniform.

Example 54 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 2.13% HUVCl0₄ (as a cathodic compound), 7.31% Ferrocene-polyol (asan anodic compound), all homogeneously dispersed in a combination ofabout 82.0% propylene carbonate (as plasticizer) and, in combination asa monomer component, about 1.57% HDT (an isocyanate) and about 1.88%Lexorez 1931-50 (a polyol), and about 0.82% polymethyl methacrylate, andabout 0.013% T−1 (a tin catalyst), and about 4.31% Uvinul N 35 (a UVstabilizer). We thoroughly mixed this monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Mirror assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″×10″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 54(A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 54(A), supra, wasuniformly applied within the mirror assemblies of Example 54(B), supra,we placed the assemblies overnight at room temperature during which timethe Monomer composition reacted to form in situ the solid polymer matrixfilm inside the mirror. These mirror assemblies were then placed in anelectrically heated convection oven maintained at about 80° C. for about2 hours.

Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 70.8% reflectance which decreased to a lowreflectance of about 9.6% when about 1.4 volts was applied to thereto.We made this determination by the reflectometer described in Example 1,supra. We noted the bleaching to be uniform.

Example 55

In this example, we chose to illustrate the beneficial properties andcharacteristics of the polychromic solid films manufactured withinelectrochromic glazings, or that may be used as small area transmissivedevices, such as optical filters and the like.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.80% HUVCl0₄ (as a cathodic compound), about 0.87% EVCl0₄ (as acathodic compound), about 1.10% Ferrocene-polyol (as an anodiccompound), about 0.086% Ferrocene (as an anodic compound), about 0.49%DMPA (as an anodic compound), all homogeneously dispersed in acombination of about 24.16% propylene carbonate (as plasticizer) and, incombination as a monomer component, about 9.70% HDT (an isocyanate) andabout 58.0% Lexorez 1931-50 (a polyol), and about 0.23% polymethylmethacrylate and about 0.014% T−I (a tin catalyst), and about 4.60%Uvinul N 35 (a UV stabilizer). We thoroughly mixed this monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Glazing Assembly with Electrochromic Monomer Composition

In this example, we assembled electrochromic glazings from clear TEC 15glass substrates (where the conductive surface of each glass substratefaced one another), with the glass having a sheet resistance of about 15ohms per square. The dimensions of the glazing assemblies were about3.0″×10″×150 μm.

We placed into these glazing assemblies the electrochromic monomercomposition of Example 55(A), supra.

C. Transformation of Electrochromic Monomer Composition within Glazingto Polychromic Solid Film

Once the electrochromic monomer composition of Example 55(A), supra, wasuniformly applied within the glazing assemblies of Example 55(B), supra,we placed the assemblies in an electrically heated convection ovenmaintained at about 80° C. for about 2 hours whereupon the monomercomposition reacted to form in situ the solid polymer matrix film insidethe glazing assemblies.

Use of Electrochromic Glazing

We applied a potential of about 1.4 volts to one of the electrochromicglazings of Example 55(B and C), supra, We observed that theelectrochromic glazings colored rapidly and uniformly to a gray colorwith greenish hue.

In addition, we observed that the high transmission at the centerportion of the glazing was about 70.8%, transmission which decreased toa low transmission of about 12.9% when about 1.4 volts was applied tothereto. We made this determination by the reflectometer described inExample 1, supra. We noted the bleaching to be uniform.

Example 56 A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 0.80% HUVlO₄ (as a cathodic compound), about 0.87% EVCl0₄ (as acathodic compound), about 1.10% Ferrocene-polyol (as an anodiccompound), about 0.086% Ferrocene (as an anodic compound), about 0.49%DMPA (as an anodic compound), all homogeneously dispersed in acombination of about 24.16% propylene carbonate (as plasticizer) and, incombination as a monomer component, about 9.70% HDT (an isocyanate) andabout 58.0% Lexorez 1931-50 (a polyol), and about 0.23% polymethylmethacrylate and about 0.014% T−1 (a tin catalyst), and about 4.60%Uvinul N 35 (a UV stabilizer). We thoroughly mixed this monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors from TEC-15glass substrates (where the conductive surface of each glass substratefaced one another), with both the clear, front glass and the silvered,rear glass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5″-xio″×105 μm, with aweather barrier of an epoxy resin coupled with spacers of about 105 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 56(A), supra, using the vacuum back fillingtechnique (as described in Varaprasad III, supra).

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 56(A), supra, wasuniformly applied within the mirror assemblies of Example 56(B), supra,we placed the assemblies overnight at room temperature during which timethe monomer composition reacted to form in situ the solid polymer matrixfilm inside the mirror. These mirror assemblies were then placed in anelectrically heated convection oven maintained at about 80° C. for about2 hours.

Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors, and observed this mirror to color rapidly and uniformly to agray color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 69.7% reflectance which decreased to a lowreflectance of about 8.7% when about 1.4 volts was applied to thereto.We made this determination by the reflectometer described in Example 1,supra. We noted the bleaching to be uniform.

While we have provided the above examples of the foregoing invention forillustrative purposes employing preferred electrochromic compounds,monomer components and plasticizers, and other components it is to beunderstood that variations and equivalents of each of the preparedelectrochromic monomer compositions identified herein will providesuitable, if not comparable, results when viewed in connection with theresults gleaned from these examples. Without undue experimentation,those of ordinary skill in the art will find it readily apparent toprepare polychromic solid film with the beneficial properties andcharacteristics desirable for the specific application armed with theteaching herein disclosed. And, it is intended that such equivalents beencompassed by the claims which follow hereinafter.

1. An exterior reflective mirror element suitable for use in an exterior rearview mirror assembly for a vehicle, said exterior reflective mirror element comprising: a transparent glass substrate having a reflector disposed on a surface thereof; wherein said reflector comprises at least one metallic reflective layer; wherein said substrate comprises a rear substrate of an electrochromic reflective mirror element; a visual indicator display disposed to the rear of said substrate; said visual indicator display being part of a blind spot detection and display system of the vehicle equipped with the exterior reflective mirror element, and wherein said visual indicator display is actuated to emit light responsive to a detection by a blind spot detection detector of the equipped vehicle of an overtaking vehicle in a side lane adjacent the side of the equipped vehicle; wherein light emitted by said visual indicator display passes through said substrate to be viewed by a driver of the equipped vehicle; wherein said visual indicator display comprises at least a first indicator at a first location to the rear of said exterior reflective mirror element; wherein said first indicator comprises a first light source at said first location; wherein a first portion of said at least one metallic reflective layer is at least partially removed by laser scribing at said first location in order to establish an at least partially transmissive first portion of said exterior reflective mirror element at said first location; wherein said first indicator comprises an icon indicative of detection by a blind spot detection and display system of the equipped vehicle of an overtaking vehicle in a side lane adjacent the side of the equipped vehicle; wherein another visual indicator display is disposed to the rear of said substrate at a second location, said another visual indicator display being part of a turn signaling system of the equipped vehicle and wherein said another visual indicator display is actuated to emit light upon actuation by the driver of a turn signal of the equipped vehicle and wherein light emitted by said another visual indicator display passes through said substrate at said second location; and wherein a second portion of said at least one metallic reflective layer is at least partially removed by laser scribing at a second location in order to establish an at least partially transmissive second portion of said exterior reflective mirror element at said second location. 